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Sample records for catalytic hydrogen generation

  1. Catalytic partial oxidation of methanol and ethanol for hydrogen generation.

    Science.gov (United States)

    Hohn, Keith L; Lin, Yu-Chuan

    2009-01-01

    Hydrogen-powered fuel cell vehicles feature high energy efficiency and minor environmental impact. Liquid fuels are ideal hydrogen carriers, which can catalytically be converted into syngas or hydrogen to power vehicles. Among the potential liquid fuels, alcohols have several advantages. The hydrogen/carbon ratio is higher than that of other liquid hydrocarbons or oxygenates, especially in the case of methanol. In addition, alcohols can be derived from renewable biomass resources. Catalytic partial oxidation of methanol or ethanol offers immense potential for onboard hydrogen generation due to its rapid reaction rate and exothermic nature. These benefits stimulate a burgeoning research community in catalyst design, reaction engineering, and mechanistic investigation. The purpose of this Minireview is to provide insight into syngas and hydrogen production from methanol and ethanol partial oxidation, particularly highlighting catalytic chemistry.

  2. Catalytic gasification of automotive shredder residues with hydrogen generation

    Science.gov (United States)

    Lin, Kuen-Song; Chowdhury, Sujan; Wang, Ze-Ping

    Hydrogen is a clean and new energy carrier to generate power through the Proton exchange membrane fuel cell (PEMFC) system. Hydrogen can be effectively turned out through the catalytic gasification of organic material such as automotive shredder residues (ASR). The main objective of this manuscript is to present an analysis of the catalytic gasification of ASR for the generation of high-purity hydrogen in a lab-scale fixed-bed downdraft gasifier using 15 wt.% NiO/Al 2O 3 catalysts at 760-900 K. In the catalytic gasification process, reduction of Ni(II) catalyst into Ni(0) has been confirmed through XANES spectra and consequently EXAFS data shows that the central Ni atoms have Ni-O and Ni-Ni bonds with bond distances of 2.03 ± 0.05 and 2.46 ± 0.05 Å, respectively. ASR is partially oxidized and ultimately converts into hydrogen rich syngas (CO and H 2) and increases of the reaction temperature are favored the generation of hydrogen with decomposition of the CO. As well, approximately 220 kg h -1 of ASR would be catalytically gasified at 760-900 K and 46.2 atm with the reactor volume 0.27 m 3 to obtain approximately 3.42 × 10 5 kcal h -1 of thermal energy during over 87% syngas generation with the generation of 100 kW electric powers.

  3. DWPF CATALYTIC HYDROGEN GENERATION PROGRAM - REVIEW OF CURRENT STATUS

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D.

    2009-07-10

    Significant progress has been made in the past two years in improving the understanding of acid consumption and catalytic hydrogen generation during the Defense Waste Processing Facility (DWPF) processing of waste sludges in the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME). This report reviews issues listed in prior internal reviews, describes progress with respect to the recommendations made by the December 2006 external review panel, and presents a summary of the current understanding of catalytic hydrogen generation in the DWPF Chemical Process Cell (CPC). Noble metals, such as Pd, Rh, and Ru, are historically known catalysts for the conversion of formic acid into hydrogen and carbon dioxide. Rh, Ru, and Pd are present in the DWPF SRAT feed as by-products of thermal neutron fission of {sup 235}U in the original waste. Rhodium appears to become most active for hydrogen as the nitrite ion concentration becomes low (within a factor of ten of the Rh concentration). Prior to hydrogen generation, Rh is definitely active for nitrite destruction to N{sub 2}O and potentially active for nitrite to NO formation. These reactions are all consistent with the presence of a nitro-Rh complex catalyst, although definite proof for the existence of this complex during Savannah River Site (SRS) waste processing does not exist. Ruthenium does not appear to become active for hydrogen generation until nitrite destruction is nearly complete (perhaps less nitrite than Ru in the system). Catalytic activity of Ru during nitrite destruction is significantly lower than that of either Rh or Pd. Ru appears to start activating as Rh is deactivating from its maximum catalytic activity for hydrogen generation. The slow activation of the Ru, as inferred from the slow rate of increase in hydrogen generation that occurs after initiation, may imply that some species (perhaps Ru itself) has some bound nitrite on it. Ru, rather than Rh, is primarily responsible for the

  4. Method of generating hydrogen by catalytic decomposition of water

    Science.gov (United States)

    Balachandran, Uthamalingam; Dorris, Stephen E.; Bose, Arun C.; Stiegel, Gary J.; Lee, Tae-Hyun

    2002-01-01

    A method for producing hydrogen includes providing a feed stream comprising water; contacting at least one proton conducting membrane adapted to interact with the feed stream; splitting the water into hydrogen and oxygen at a predetermined temperature; and separating the hydrogen from the oxygen. Preferably the proton conducting membrane comprises a proton conductor and a second phase material. Preferable proton conductors suitable for use in a proton conducting membrane include a lanthanide element, a Group VIA element and a Group IA or Group IIA element such as barium, strontium, or combinations of these elements. More preferred proton conductors include yttrium. Preferable second phase materials include platinum, palladium, nickel, cobalt, chromium, manganese, vanadium, silver, gold, copper, rhodium, ruthenium, niobium, zirconium, tantalum, and combinations of these. More preferably second phase materials suitable for use in a proton conducting membrane include nickel, palladium, and combinations of these. The method for generating hydrogen is preferably preformed in the range between about 600.degree. C. and 1,700.degree. C.

  5. Formic Acid Free Flowsheet Development To Eliminate Catalytic Hydrogen Generation In The Defense Waste Processing

    Energy Technology Data Exchange (ETDEWEB)

    Lambert, Dan P.; Stone, Michael E.; Newell, J. David; Fellinger, Terri L.; Bricker, Jonathan M.

    2012-09-14

    The Defense Waste Processing Facility (DWPF) processes legacy nuclear waste generated at the Savannah River Site (SRS) during production of plutonium and tritium demanded by the Cold War. The nuclear waste is first treated via a complex sequence of controlled chemical reactions and then vitrified into a borosilicate glass form and poured into stainless steel canisters. Converting the nuclear waste into borosilicate glass canisters is a safe, effective way to reduce the volume of the waste and stabilize the radionuclides. Testing was initiated to determine whether the elimination of formic acid from the DWPF's chemical processing flowsheet would eliminate catalytic hydrogen generation. Historically, hydrogen is generated in chemical processing of alkaline High Level Waste sludge in DWPF. In current processing, sludge is combined with nitric and formic acid to neutralize the waste, reduce mercury and manganese, destroy nitrite, and modify (thin) the slurry rheology. The noble metal catalyzed formic acid decomposition produces hydrogen and carbon dioxide. Elimination of formic acid by replacement with glycolic acid has the potential to eliminate the production of catalytic hydrogen. Flowsheet testing was performed to develop the nitric-glycolic acid flowsheet as an alternative to the nitric-formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be reduced and removed by steam stripping in DWPF with no catalytic hydrogen generation. All processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Ten DWPF tests were performed with nonradioactive simulants designed to cover a broad compositional range. No hydrogen was generated in testing without formic acid.

  6. Review of Catalytic Hydrogen Generation in the DWPF Chemical Processing Cell, Part II

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, David C.; Lambert, Daniel P.; Baich, Mark A.

    2005-08-01

    The Savannah River National Laboratory is in the process of investigating factors suspected of impacting catalytic hydrogen generation in the Defense Waste Processing Facility, DWPF, Chemical Process Cell, CPC. Noble metal catalyzed hydrogen generation in simulation work constrains the allowable acid addition operating window in DWPF. This constraint potentially impacts washing strategies during sludge batch preparation. It can also influence decisions related to the addition of secondary waste streams to a sludge batch. Catalytic hydrogen generation data from 2002-2005 were reviewed. The data came from process simulations of the DWPF Sludge Receipt and Adjustment Tank, SRAT, and Slurry Mix Evaporator, SME. Most of the data was from the development work for the Sludge Batch 3 process flowsheet. This included simulant and radioactive waste testing. Preliminary Sludge Batch 4 data were also reviewed. A statistical analysis of SB3 simulant hydrogen generation data was performed. One factor considered in the statistical analysis was excess acid. Excess acid was determined experimentally as the acid added beyond that required to achieve satisfactory nitrite destruction.

  7. Review of Catalytic Hydrogen Generation in the Defense Waste Processing Facility (DWPF) Chemical Processing Cell

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D. C.

    2004-12-31

    This report was prepared to fulfill the Phase I deliverable for HLW/DWPF/TTR-98-0018, Rev. 2, ''Hydrogen Generation in the DWPF Chemical Processing Cell'', 6/4/2001. The primary objective for the preliminary phase of the hydrogen generation study was to complete a review of past data on hydrogen generation and to prepare a summary of the findings. The understanding was that the focus should be on catalytic hydrogen generation, not on hydrogen generation by radiolysis. The secondary objective was to develop scope for follow-up experimental and analytical work. The majority of this report provides a summary of past hydrogen generation work with radioactive and simulated Savannah River Site (SRS) waste sludges. The report also includes some work done with Hanford waste sludges and simulants. The review extends to idealized systems containing no sludge, such as solutions of sodium formate and formic acid doped with a noble metal catalyst. This includes general information from the literature, as well as the focused study done by the University of Georgia for the SRS. The various studies had a number of points of universal agreement. For example, noble metals, such as Pd, Rh, and Ru, catalyze hydrogen generation from formic acid and formate ions, and more acid leads to more hydrogen generation. There were also some points of disagreement between different sources on a few topics such as the impact of mercury on the noble metal catalysts and the identity of the most active catalyst species. Finally, there were some issues of potential interest to SRS that apparently have not been systematically studied, e.g. the role of nitrite ion in catalyst activation and reactivity. The review includes studies covering the period from about 1924-2002, or from before the discovery of hydrogen generation during simulant sludge processing in 1988 through the Shielded Cells qualification testing for Sludge Batch 2. The review of prior studies is followed by a

  8. Marrying gas power and hydrogen energy: A catalytic system for combining methane conversion and hydrogen generation

    NARCIS (Netherlands)

    Beckers, J.; Gaudillère, C.; Farrusseng, D.; Rothenberg, G.

    2009-01-01

    Ceria-based catalysts are good candidates for integrating methane combustion and hydrogen generation. These new, tuneable catalysts are easily prepared. They are robust inorganic crystalline materials, and perform well at the 400 °C-550 °C range, in some cases even without precious metals. This

  9. CATALYTIC INTERACTIONS OF RHODIUM, RUTHENIUM, AND MERCURY DURING SIMULATED DWPF CPC PROCESSING WITH HYDROGEN GENERATION

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-10-09

    Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell (CPC) vessels were performed as part of the ongoing investigation into catalytic hydrogen generation. Rhodium, ruthenium, and mercury have been identified as the principal elemental factors affecting the peak hydrogen generation rate in the DWPF Sludge Receipt and Adjustment Tank (SRAT) for a given acid addition. The primary goal of this study is to identify any significant interactions between the three factors. Noble metal concentrations were similar to recent sludge batches. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%. An experimental matrix was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), two duplicate midpoint runs, and two additional replicate runs to assess reproducibility away from the midpoint. Midpoint testing can identify potential quadratic effects from the three factors. A single sludge simulant was used for all tests. Acid addition was kept effectively constant except to compensate for variations in the starting mercury concentration. Six Slurry Mix Evaporator (SME) cycles were performed to supplement the SME hydrogen generation database. Some of the preliminary findings from this study include: (1) Rh was linked to the maximum SRAT hydrogen generation rate in the first two hours after acid addition in preliminary statistical modeling. (2) Ru was linked conclusively to the maximum SRAT hydrogen generation rate in the last four hours of reflux in preliminary statistical modeling. (3) Increasing the ratio of Hg/Rh shifted the noble metal controlling the maximum SRAT hydrogen generation rate from

  10. Catalytic hydrolysis of ammonia borane for hydrogen generation using cobalt nanocluster catalyst supported on polydopamine functionalized multiwalled carbon nanotube

    International Nuclear Information System (INIS)

    Arthur, Ernest Evans; Li, Fang; Momade, Francis W.Y.; Kim, Hern

    2014-01-01

    Hydrogen was generated from ammonia borane complex by hydrolysis using cobalt nanocluster catalyst supported on polydopamine functionalized MWCNTs (multi-walled carbon nanotubes). The impregnation-chemical reduction method was used for the preparation of the supported catalyst. The nanocluster catalyst support was formed by in-situ oxidative polymerization of dopamine on the MWCNTs in alkaline solution at room temperature. The structural and physical–chemical properties of the nanocluster catalyst were characterized by FT-IR (Fourier transform infrared spectroscopy), EDX (energy-dispersive X-ray spectroscopy), SEM (scanning electron microscope), XRD (X-ray diffraction) and TEM (transmission electron microscopy). The nanocluster catalyst showed good catalytic activity for the hydrogen generation from aqueous ammonia borane complex. A reusability test to determine the practical usage of the catalyst was also investigated. The result revealed that the catalyst maintained an appreciable catalytic performance and stability in terms of its reusability after three cycle of reuse for the hydrolysis reaction. Also, the activation energy for the hydrolysis of ammonia borane complex was estimated to be 50.41 kJmol −1 , which is lower than the values of some of the reported catalyst. The catalyst can be considered as a promising candidate in developing highly efficient portable hydrogen generation systems such as PEMFC (proton exchange membrane fuel cells). - Highlights: • Co/Pdop-o-MWCNT (Pdop functionalized MWCNT supported cobalt nanocluster) catalyst was synthesized for hydrogen generation. • It is an active catalyst for hydrogen generation via hydrolysis of ammonia borane. • It showed good stability in terms of reusability for the hydrogen generation

  11. Catalytic autothermal reforming of diesel fuel for hydrogen generation in fuel cells. I. Activity tests and sulfur poisoning

    Science.gov (United States)

    Cheekatamarla, Praveen K.; Lane, Alan M.

    Polymer electrolyte membrane (PEM) fuel cells require hydrogen as the fuel source for generating power. Hydrogen can be produced in a fuel processor by the catalytic reforming of hydrocarbons. The objective of this paper is to present an analysis of the autothermal reforming (ATR) of synthetic diesel fuel in an adiabatic reactor using a Pt/ceria catalyst. ATR combines endothermic steam reforming and exothermic partial oxidation reactions in a single unit. This simple system provides higher efficiency and higher energy density than other conventional processes. The product composition as a function of the operating variables and the temperature and concentration profile inside the reactor were studied. Hydrogen was generated under adiabatic conditions by heating the feed mixture and ATR reactor to only 400 °C in contrast to higher temperatures reported in the literature. The stability of the catalyst and its response to the presence of S poison was also investigated.

  12. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

    KAUST Repository

    Shinagawa, Tatsuya

    2015-01-01

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction. This journal is © the Owner Societies.

  13. Hydrogen peroxide catalytic decomposition

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2010-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

  14. Electro-catalytic conversion of ethanol in solid electrolyte cells for distributed hydrogen generation

    International Nuclear Information System (INIS)

    Ju, HyungKuk; Giddey, Sarbjit; Badwal, Sukhvinder P.S.; Mulder, Roger J.

    2016-01-01

    Highlights: • Ethanol assisted water electrolysis reduces electric energy input by more than 50%. • Partial oxidation of ethanol leads to formation of undesired chemicals. • Degradation occurs due to formation of by-products and poisoning of catalyst. • Better catalyst has the potential to increase ethanol to H 2 conversion efficiency. • A plausible ethanol electro-oxidation mechanism has been proposed - Abstract: The global interest in hydrogen/fuel cell systems for distributed power generation and transport applications is rapidly increasing. Many automotive companies are now bringing their pre-commercial fuel cell vehicles in the market, which will need extensive hydrogen generation, distribution and storage infrastructure for fueling of these vehicles. Electrolytic water splitting coupled to renewable sources offers clean on-site hydrogen generation option. However, the process is energy intensive requiring electric energy >4.2 kWh for the electrolysis stack and >6 kWh for the complete system per m 3 of hydrogen produced. This paper investigates using ethanol as a renewable fuel to assist with water electrolysis process to substantially reduce the energy input. A zero-gap cell consisting of polymer electrolyte membrane electrolytic cells with Pt/C and PtSn/C as anode catalysts were employed. Current densities up to 200 mA cm −2 at 70 °C were achieved at less than 0.75 V corresponding to an energy consumption of about 1.62 kWh m −3 compared with >4.2 kWh m −3 required for conventional water electrolysis. Thus, this approach for hydrogen generation has the potential to substantially reduce the electric energy input to less than 40% with the remaining energy provided by ethanol. However, due to performance degradation over time, the energy consumption increased and partial oxidation of ethanol led to lower conversion efficiency. A plausible ethanol electro-oxidation mechanism has been proposed based on the Faradaic conversion of ethanol and mass

  15. Controllable pneumatic generator based on the catalytic decomposition of hydrogen peroxide

    Science.gov (United States)

    Kim, Kyung-Rok; Kim, Kyung-Soo; Kim, Soohyun

    2014-07-01

    This paper presents a novel compact and controllable pneumatic generator that uses hydrogen peroxide decomposition. A fuel micro-injector using a piston-pump mechanism is devised and tested to control the chemical decomposition rate. By controlling the injection rate, the feedback controller maintains the pressure of the gas reservoir at a desired pressure level. Thermodynamic analysis and experiments are performed to demonstrate the feasibility of the proposed pneumatic generator. Using a prototype of the pneumatic generator, it takes 6 s to reach 3.5 bars with a reservoir volume of 200 ml at the room temperature, which is sufficiently rapid and effective to maintain the repetitive lifting of a 1 kg mass.

  16. Base-free hydrogen generation from methanol using a bi-catalytic system.

    Science.gov (United States)

    Monney, Angèle; Barsch, Enrico; Sponholz, Peter; Junge, Henrik; Ludwig, Ralf; Beller, Matthias

    2014-01-21

    A bi-catalytic system, in which Ru-MACHO-BH and Ru(H)2(dppe)2 interact in a synergistic manner, was developed for the base-free dehydrogenation of methanol. A total TON > 4200 was obtained with only trace amounts of CO contamination (<8 ppm) in the produced gas.

  17. Catalytic Hydrolysis of Ammonia Borane by Cobalt Nickel Nanoparticles Supported on Reduced Graphene Oxide for Hydrogen Generation

    Directory of Open Access Journals (Sweden)

    Yuwen Yang

    2014-01-01

    Full Text Available Well dispersed magnetically recyclable bimetallic CoNi nanoparticles (NPs supported on the reduced graphene oxide (RGO were synthesized by one-step in situ coreduction of aqueous solution of cobalt(II chloride, nickel (II chloride, and graphite oxide (GO with ammonia borane (AB as the reducing agent under ambient condition. The CoNi/RGO NPs exhibits excellent catalytic activity with a total turnover frequency (TOF value of 19.54 mol H2 mol catalyst−1 min−1 and a low activation energy value of 39.89 kJ mol−1 at room temperature. Additionally, the RGO supported CoNi NPs exhibit much higher catalytic activity than the monometallic and RGO-free CoNi counterparts. Moreover, the as-prepared catalysts exert satisfying durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB, which make the practical reusing application of the catalysts more convenient. The usage of the low-cost, easy-getting catalyst to realize the production of hydrogen under mild condition gives more confidence for the application of ammonia borane as a hydrogen storage material. Hence, this general method indicates that AB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to facile preparation of other RGO-based metallic systems.

  18. Design and assembly of a catalyst bed gas generator for the catalytic decomposition of high concentration hydrogen peroxide propellants and the catalytic combustion of hydrocarbon/air mixtures

    Science.gov (United States)

    Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Sevener, Kathleen M. (Inventor)

    2004-01-01

    A method for designing and assembling a high performance catalyst bed gas generator for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The gas generator utilizes a sectioned catalyst bed system, and incorporates a robust, high temperature mixed metal oxide catalyst. The gas generator requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. The high performance catalyst bed gas generator system has consistently demonstrated high decomposition efficiency, extremely low decomposition roughness, and long operating life on multiple test articles.

  19. Catalytic hydrogen recombination for nuclear containments

    International Nuclear Information System (INIS)

    Koroll, G.W.; Lau, D.W.P.; Dewit, W.A.; Graham, W.R.C.

    1994-01-01

    Catalytic recombiners appear to be a credible option for hydrogen mitigation in nuclear containments. The passive operation, versatility and ease of back fitting are appealing for existing stations and new designs. Recently, a generation of wet-proofed catalyst materials have been developed at AECL which are highly specific to H 2 -O 2 , are active at ambient temperatures and are being evaluated for containment applications. Two types of catalytic recombiners were evaluated for hydrogen removal in containments based on the AECL catalyst. The first is a catalytic combustor for application in existing air streams such as provided by fans or ventilation systems. The second is an autocatalytic recombiner which uses the enthalpy of reaction to produce natural convective flow over the catalyst elements. Intermediate-scale results obtained in 6 m 3 and 10 m 3 spherical and cylindrical vessels are given to demonstrate self-starting limits, operating limits, removal capacity, scaling parameters, flow resistance, mixing behaviour in the vicinity of an operating recombiner and sensitivity to poisoning, fouling and radiation. (author). 13 refs., 10 figs

  20. Catalytic glycerol steam reforming for hydrogen production

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  1. Preparation and characterization of LTA-type zeolite framework dispersed ruthenium nanoparticles and their catalytic application in the hydrolytic dehydrogenation of ammonia–borane for efficient hydrogen generation

    International Nuclear Information System (INIS)

    Zahmakiran, Mehmet

    2012-01-01

    Highlights: ► Ru(0)NPs-ZK-4 were prepared and characterized by advanced analytical techniques. ► They achieve the hydrolysis of ammonia-borane with TOF = 5410 h −1 and TTO = 36700. ► They maintain 85% of their activity even at the fifth catalytic run. - Abstract: The safe and efficient hydrogen storage and production are major obstacles to use hydrogen as an energy carrier. Therefore, significant efforts have been focused on the development of new materials for the chemical hydrogen storage and production. Of particular importance, ammonia–borane (NH 3 BH 3 ) is emerging as one of the most promising solid hydrogen carrier due to its high gravimetric hydrogen storage capacity (19.6 wt.%) and low molecular weight (30.8 g/mol). ammonia–borane can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, the discovery of a new catalytic material, ruthenium nanoparticles stabilized by ZK-4 zeolite framework, for this important reaction has been reported. This new catalyst system was prepared by borohydride reduction of ruthenium(III)-exchanged ZK-4 zeolite in water at room temperature. The characterization of the resulting material by advanced analytical tools shows the formation of ZK-4 zeolite dispersed ruthenium nanoparticles (2.9 ± 0.9 nm). The catalytic performance of the resulting supported ruthenium nanoparticles depending on activity, lifetime and reusability was demonstrated in the hydrolytic dehydrogenation of ammonia–borane. They were found to be highly active (initial TOF = 5410 h −1 ), long-lived (TTO = 36,700) and reusable catalyst (retaining of >85% of initial activity in the 5th reuse) in this important catalytic reaction at room temperature under air.

  2. THEORETICAL STUDY OF CATALYTIC HYDROGENATION OF ...

    African Journals Online (AJOL)

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    Catalytic hydrotreating process is a technique of purification of the crude oil with the aim of the improvement of the quality and the stability of fuels and lubricants. This is performed by the destruction of heterocyclic compounds and by the saturation of unsaturated hydrocarbons under the effect of the hydrogen pressure in ...

  3. Advanced Catalytic Hydrogenation Retrofit Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Reinaldo M. Machado

    2002-08-15

    Industrial hydrogenation is often performed using a slurry catalyst in large stirred-tank reactors. These systems are inherently problematic in a number of areas, including industrial hygiene, process safety, environmental contamination, waste production, process operability and productivity. This program proposed the development of a practical replacement for the slurry catalysts using a novel fixed-bed monolith catalyst reactor, which could be retrofitted onto an existing stirred-tank reactor and would mitigate many of the minitations and problems associated with slurry catalysts. The full retrofit monolith system, consisting of a recirculation pump, gas/liquid ejector and monolith catalyst, is described as a monolith loop reactor or MLR. The MLR technology can reduce waste and increase raw material efficiency, which reduces the overall energy required to produce specialty and fine chemicals.

  4. Enhanced catalytic performance in hydrogen generation from NaBH4 hydrolysis by super porous cryogel supported Co and Ni catalysts

    Science.gov (United States)

    Seven, Fahriye; Sahiner, Nurettin

    2014-12-01

    The neutral 3-D superporous cryogel is prepared from a poly(acrylamide) (p(AAm)) hydrogel network modified with an amidoximation reaction to induce chemical changes to produce superporous amidoximated-p(AAm) (amid-p(AAm)) cryogel. The newly-formed strongly ionizable matrices can readily absorb metal ions such as Co(II) and Ni(II) enabling in situ preparation of corresponding metal nanoparticles by NaBH4 treatments. It is found that the superporous amid-p(AAm)-Co cryogel composite is very effective as a catalyst for H2 generation from hydrolysis of NaBH4 in alkaline medium. Furthermore, it is demonstrated that the metal ion loading capacity and catalytic activity of superporous amid-p(AAm)-Co cryogel composites increased with 2nd and 3rd Co(II) ion loading and reduction cycles. The hydrogen generation rate of p(AAm)-Co metal composites is increased to 1926.3 ± 1.1 from 1130.2 ± 1.5 (mL H2) (min)-1 (g of M)-1. The effect of various parameters such as porosity, metal type, the number of reloading and reduction cycles of the metal ion, and temperature are investigated for the hydrolysis of NaBH4. The kinetic parameters such as energy, enthalpy and entropy are determined as Ea = 39.7 ± 0.2 kJ mol-1, ΔH = 37.2 ± 0.1 kJ mol-1 and ΔS = -171.9 ± 0.5 J mol-1 K-1, respectively.

  5. High purity hydrogen generator for on-site hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Jaesung Han; Il-Su Kim; Keun-Seob Choi [Taedok Institute of Technology, Taejon (Korea)

    2002-10-01

    We report a compact on-site hydrogen generator, which produces 10 Nm{sup 3}/h of 99.9995% or higher purity hydrogen from methanol water mixture. This system consists of a methanol steam reformer to get hydrogen rich reformed gas and a metal membrane purification module to recover high purity hydrogen from the reformed gas. It can be used either as the on-site hydrogen supplier for industries or as the fuel processor for fuel cells. The hydrogen recovery by the metal membrane is about 75%, and the remaining 25% of hydrogen is recycled and burned in the catalytic combustion zone to supply heat for the endothermic steam reforming reaction. The overall thermal efficiency of the system is calculated to be 82% based on high heating values of methanol feed and product hydrogen. (author)

  6. Make the most of catalytic hydrogenations

    Energy Technology Data Exchange (ETDEWEB)

    Landert, J.P.; Scubla, T. [Biazzi S.A., Chailly-Montreux (Switzerland)

    1995-03-01

    Liquid-phase catalytic hydrogenation is one of the most useful and versatile reactions available for organic synthesis. Because it is environmentally clean, it has replaced other reduction processes, such as the Bechamp reaction, and zinc and sulfide reductions. Moreover, the economics are favorable, provided that raw materials free of catalyst poisons are used. The hydrogenation reaction is very selective with appropriate catalysts and can often be carried out without a solvent. Applications include reduction of unsaturated carbon compounds to saturated derivatives (for example, in vegetable-oil processing), carbonyl compounds to alcohols (such as sorbitol), and nitrocompounds to amines. the reactions are usually run in batch reactors to rapidly reach complete conversion and allow quick change-over of products. The paper describes the basics of hydrogenation; steering clear of process hazards; scale-up and optimization; and system design in practice.

  7. Electrochemical Hydrogen Peroxide Generator

    Science.gov (United States)

    Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

    2010-01-01

    Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials

  8. Microchannel Reactor System for Catalytic Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-22

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

  9. Catalytic activity of noble metals promoting hydrogen uptake

    NARCIS (Netherlands)

    Borgschulte, A.; Westerwaal, R.J.; Rector, J.H.; Schreuders, H.; Dam, B.; Griessen, R.P.

    2006-01-01

    The engineering of pure and metal alloy catalysts for hydrogen absorption is needed to improve the kinetics of hydrogen-related devices. We introduce a new route to search for alloys that can yield superior catalytic behavior for hydrogen absorption, using an optical technique to measure the

  10. Hydrogen storage and generation system

    Science.gov (United States)

    Dentinger, Paul M.; Crowell, Jeffrey A. W.

    2010-08-24

    A system for storing and generating hydrogen generally and, in particular, a system for storing and generating hydrogen for use in an H.sub.2/O.sub.2 fuel cell. The hydrogen storage system uses the beta particles from a beta particle emitting material to degrade an organic polymer material to release substantially pure hydrogen. In a preferred embodiment of the invention, beta particles from .sup.63Ni are used to release hydrogen from linear polyethylene.

  11. Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: An integrated process for ZnO reduction and zinc nanostructures fabrication

    International Nuclear Information System (INIS)

    Maciel, Adriana Veloso; Job, Aldo Eloizo; Nova Mussel, Wagner da; Brito, Walter de; Duarte Pasa, Vanya Marcia

    2011-01-01

    The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor-solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H 2 when compared to pure cellulose. The process was also carried out in a tubular furnace with N 2 atmosphere, at temperatures up to 900 o C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.

  12. Microscale Synthesis of Chiral Alcohols via Asymmetric Catalytic Transfer Hydrogenation

    Science.gov (United States)

    Peeters, Christine M.; Deliever, Rik; De Vos, Dirk

    2009-01-01

    Synthesis of pure enantiomers is a key issue in industry, especially in areas connected to life sciences. Catalytic asymmetric synthesis has emerged as a powerful and practical tool. Here we describe an experiment on racemic reduction and asymmetric reduction via a catalytic hydrogen transfer process. Acetophenone and substituted acetophenones are…

  13. Method for low temperature catalytic production of hydrogen

    Science.gov (United States)

    Mahajan, Devinder

    2003-07-22

    The invention provides a process for the catalytic production of a hydrogen feed by exposing a hydrogen feed to a catalyst which promotes a base-catalyzed water-gas-shift reaction in a liquid phase. The hydrogen feed can be provided by any process known in the art of making hydrogen gas. It is preferably provided by a process that can produce a hydrogen feed for use in proton exchange membrane fuel cells. The step of exposing the hydrogen feed takes place preferably from about 80.degree. C. to about 150.degree. C.

  14. How absorbed hydrogen affects the catalytic activity of transition metals.

    Science.gov (United States)

    Aleksandrov, Hristiyan A; Kozlov, Sergey M; Schauermann, Swetlana; Vayssilov, Georgi N; Neyman, Konstantin M

    2014-12-01

    Heterogeneous catalysis is commonly governed by surface active sites. Yet, areas just below the surface can also influence catalytic activity, for instance, when fragmentation products of catalytic feeds penetrate into catalysts. In particular, H absorbed below the surface is required for certain hydrogenation reactions on metals. Herein, we show that a sufficient concentration of subsurface hydrogen, H(sub) , may either significantly increase or decrease the bond energy and the reactivity of the adsorbed hydrogen, H(ad) , depending on the metal. We predict a representative reaction, ethyl hydrogenation, to speed up on Pd and Pt, but to slow down on Ni and Rh in the presence of H(sub) , especially on metal nanoparticles. The identified effects of subsurface H on surface reactivity are indispensable for an atomistic understanding of hydrogenation processes on transition metals and interactions of hydrogen with metals in general. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Short hydrogen bonds in the catalytic mechanism of serine proteases

    Directory of Open Access Journals (Sweden)

    VLADIMIR LESKOVAC

    2008-04-01

    Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.

  16. Hydrogen Generation From Electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Steven Cohen; Stephen Porter; Oscar Chow; David Henderson

    2009-03-06

    Small-scale (100-500 kg H2/day) electrolysis is an important step in increasing the use of hydrogen as fuel. Until there is a large population of hydrogen fueled vehicles, the smaller production systems will be the most cost-effective. Performing conceptual designs and analyses in this size range enables identification of issues and/or opportunities for improvement in approach on the path to 1500 kg H2/day and larger systems. The objectives of this program are to establish the possible pathways to cost effective larger Proton Exchange Membrane (PEM) water electrolysis systems and to identify areas where future research and development efforts have the opportunity for the greatest impact in terms of capital cost reduction and efficiency improvements. System design and analysis was conducted to determine the overall electrolysis system component architecture and develop a life cycle cost estimate. A design trade study identified subsystem components and configurations based on the trade-offs between system efficiency, cost and lifetime. Laboratory testing of components was conducted to optimize performance and decrease cost, and this data was used as input to modeling of system performance and cost. PEM electrolysis has historically been burdened by high capital costs and lower efficiency than required for large-scale hydrogen production. This was known going into the program and solutions to these issues were the focus of the work. The program provided insights to significant cost reduction and efficiency improvement opportunities for PEM electrolysis. The work performed revealed many improvement ideas that when utilized together can make significant progress towards the technical and cost targets of the DOE program. The cell stack capital cost requires reduction to approximately 25% of today’s technology. The pathway to achieve this is through part count reduction, use of thinner membranes, and catalyst loading reduction. Large-scale power supplies are available

  17. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    International Nuclear Information System (INIS)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun

    2012-01-01

    The ruthenium(II) complex [Ru(bpy) 2 -(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus

  18. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    Energy Technology Data Exchange (ETDEWEB)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun [Pusan National University, Busan (Korea, Republic of)

    2012-01-15

    The ruthenium(II) complex [Ru(bpy){sub 2}-(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus.

  19. Hydrogen production via catalytic processing of renewable feedstocks

    International Nuclear Information System (INIS)

    Nazim Muradov; Franklyn Smith; Ali T-Raissi

    2006-01-01

    Landfill gas (LFG) and biogas can potentially become important feedstocks for renewable hydrogen production. The objectives of this work were: (1) to develop a catalytic process for direct reforming of CH 4 -CO 2 gaseous mixture mimicking LFG, (2) perform thermodynamic analysis of the reforming process using AspenPlus chemical process simulator, (3) determine operational conditions for auto-thermal (or thermo-neutral) reforming of a model CH 4 -CO 2 feedstock, and (4) fabricate and test a bench-scale hydrogen production unit. Experimental data obtained from catalytic reformation of the CH 4 -CO 2 and CH 4 -CO 2 -O 2 gaseous mixtures using Ni-catalyst were in a good agreement with the simulation results. It was demonstrated that catalytic reforming of LFG-mimicking gas produced hydrogen with the purity of 99.9 vol.%. (authors)

  20. The removal of low level in organics via electro generated hydrogen peroxide in the presence of catalytic amounts of Fe{sup 2+}

    Energy Technology Data Exchange (ETDEWEB)

    Marrosu, G.; Petrucci, R.; Trazza, A. [Rome Univ. La Sapienza (Italy). Dipt. di Ingegneria

    2001-04-01

    Low level phosphites and hypophosphites were completely converted into phosphates via hydrogen peroxide generated by cathodic reduction of oxygen in acidic aqueous medium at a reticulated vitreous carbon electrode, in the presence of little amounts of Fe{sup 2+}. The contemporary regeneration of Fe{sup 2+} by cathodic reduction of Fe{sup 3+}, produced by the well known Fenton reaction, furnishes an excellent way to continuously produce little amount of the Fenton reactive and, as a consequence, of the powerful oxidant hydroxyl radical HO. The best conditions for the complete removal of phosphorus as phosphites and hypophosphites are reported. [Italian] Fosfiti ed ipofosfiti in bassa concentrazione sono stati convertiti completamente in fosfati mediante perossido di idrogeno generato per riduzione catodica dell'ossigeno in mezzo acquoso acido su elettrodo di carbone vetroso reticolato, in presenza di piccole quantita' di Fe{sup 2+}. La contemporanea rigenerazione di Fe{sup 2+} per riduzione catodica di Fe{sup 3+}, prodotto secondo la nota reazione di Fenton, fornisce un' eccellente via per produrre in modo continuo quantita' del reattivo di Fenton, e di conseguenza, del potente ossidante radicale idrossile HO. Vengono riportate le migliori condizioni operative per la completa rimozione del fosforo presente sotto forma di fosfiti e ipofosfiti.

  1. Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Stummann, Magnus Zingler; Høj, Martin; Gabrielsen, Jostein

    2017-01-01

    due to coking of the catalyst is an inhibitive problem for this technology. The objective of the present work is to produce oxygen free gasoline and diesel from biomass by hydrogen assisted catalytic fast pyrolysis. Fast pyrolysis of beech wood has been performed in high-pressure hydrogen atmosphere......Fast pyrolysis of biomass is a well-known technology for producing bio-oil, however in order to use the oil as transportation fuel the oxygen content must be decreased from approximately 30 wt.% to below 1 wt.%. This can be achieved by catalytic hydrodeoxygenation (HDO). Unfortunately, deactivation...

  2. Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Stummann, Magnus Zingler; Høj, Martin; Schandel, Christian Bækhøj

    Fast pyrolysis of biomass is a well-known technology for producing bio-oil, however in order to use the oil as transportation fuel the oxygen content must be decreased from approximately 30 wt.% to below 1 wt.%. This can be achieved by catalytic hydrodeoxygenation (HDO). Unfortunately, deactivation...... due to coking of the catalyst is an inhibitive problem for this technology. The objective of the present work is to produce oxygen free gasoline and diesel from biomass by hydrogen assisted catalytic fast pyrolysis. Fast pyrolysis of beech wood has been performed in high-pressure hydrogen atmosphere...

  3. Effect of urea deproteinization on catalytic hydrogenation of natural rubber latex

    Science.gov (United States)

    Cifriadi, A.; Chalid, M.; Puspitasari, S.

    2017-07-01

    Natural rubber is unsaturated biopolymer which has low resistance to heat, oxygen, and ozone. Chemical modification of natural rubber by catalytic hydrogenation can improve its oxidative property. In this study, the catalytic hydrogenation of natural rubber was investigated in latex phase after reduction of protein content with urea. Hydrogenation of deproteinized natural rubber latex was performed by using diimide which generated insitu from hydrazine hydrate/hydrogen peroxide and catalyst (boric acid, cupric sulfate and cupric acetate) at 70°C for 5 h. The hydrogenation system was stabilized with sodium dodecyl sulphate. The hydrogenation of deproteinized natural rubber (HDPNR) was confirmed by FTIR analysis. The result indicated that cupric sulphate was extremely active catalyst which was showed by the elimination of C=C transmittance bands at 1660 cm-1 on HDPNR spectra and highest degree of hydrogenation. Furthermore, urea deproteinization increased possibility of side reactions during catalytic hydrogenation as seen on the reduction of gel content compared to undeproteinized natural rubber.

  4. Converting sugars to sugar alcohols by aqueous phase catalytic hydrogenation

    Science.gov (United States)

    Elliott, Douglas C [Richland, WA; Werpy, Todd A [West Richland, WA; Wang, Yong [Richland, WA; Frye, Jr., John G.

    2003-05-27

    The present invention provides a method of converting sugars to their corresponding sugar alcohols by catalytic hydrogenation in the aqueous phase. It has been found that surprisingly superior results can be obtained by utilizing a relatively low temperature (less than 120.degree. C.), selected hydrogenation conditions, and a hydrothermally stable catalyst. These results include excellent sugar conversion to the desired sugar alcohol, in combination with long life under hydrothermal conditions.

  5. High rates of catalytic hydrogen combustion with air over coated ...

    Indian Academy of Sciences (India)

    BHASKAR DEVU MUKRI

    2017-08-02

    Aug 2, 2017 ... High rates of catalytic hydrogen combustion with air over. Ti0.97Pd0.03O2−δ coated cordierite monolith. BHASKAR DEVU MUKRI. ∗ and M S HEGDE. Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India. E-mail: bhaskardm@gmail.com. MS received 9 May 2017; ...

  6. Theoretical study of catalytic hydrogenation of oxirane and its methyl ...

    African Journals Online (AJOL)

    C3H6O) is its methyl derivative. Theoretical studies on catalytic hydrogenation of both compounds, in presence of aluminium chloride (AlCl3) catalyst, are carried out. The products of reactions are ethanol and propan-1-ol from oxirane and ...

  7. Review of literature on catalytic recombination of hydrogen--oxygen

    International Nuclear Information System (INIS)

    Homsy, R.V.; Glatron, C.A.

    1968-01-01

    The results are reported of a literature search for information concerning the heterogeneous, gas phase, catalytic hydrogen-oxygen recombination. Laboratory scale experiments to test the performance of specific metal oxide catalysts under conditions simulating the atmosphere within a nuclear reactor containment vessel following a loss-of-coolant blowdown accident are suggested

  8. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water.

    Science.gov (United States)

    Cortright, R D; Davda, R R; Dumesic, J A

    2002-08-29

    Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500 K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose -- which makes up the major energy reserves in plants and animals -- to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

  9. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water

    Science.gov (United States)

    Cortright, R. D.; Davda, R. R.; Dumesic, J. A.

    2002-08-01

    Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose-which makes up the major energy reserves in plants and animals-to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

  10. THEORETICAL STUDY OF CATALYTIC HYDROGENATION OF ...

    African Journals Online (AJOL)

    Preferred Customer

    136.427 kJ) and reaction energy (-0.107 Hartree or -270.34 kJ). This negative value of reaction energy indicates that the reaction is exoenergetic. Figures 4 and 5 show respectively the variations of some interatomic distances, calculated by HF method, and those of Mulliken atomic charges during the hydrogenation process ...

  11. Catalytic Hydrogenation of Acetone to Isopropanol: An Environmentally Benign Approach

    Directory of Open Access Journals (Sweden)

    Ateeq Rahman

    2011-01-01

    Full Text Available The catalytic hydrogenation of acetone is an important area of catalytic process to produce fine chemicals. Hydrogenation of acetone has important applications for heat pumps, fuel cells or in fulfilling the sizeable demand for the production of 2-propanol. Catalytic vapour phase hydrogenation of acetone has gained attention over the decades with variety of homogeneous catalysts notably Iridium, Rh, Ru complexes and heterogeneous catalysts comprising of Raney Nickel, Raney Sponge, Ni/Al2O3, Ni/SiO2, or Co-Al2O3, Pd, Rh, Ru, Re, or Fe/Al2O3 supported on SiO2 or MgO and even CoMgAl, NiMg Al layered double hydroxide, Cu metal, CuO, Cu2O. Nano catalysts are developed for actone reduction Ni maleate, cobalt oxide prepared in organic solvents. Author present a review on acetone hydrogenation under different conditions with various homogeneous and heterogeneous catalysts studied so far in literature and new strategies to develop economic and environmentally benign approach. ©2010 BCREC UNDIP. All rights reserved(Received: 16th June 2010, Revised: 18th October 2010; Accepted: 25th October 2010[How to Cite:Ateeq Rahman. (2010. Catalytic Hydrogenation of Acetone to Isopropanol: An Environmentally Benign Approach. Bulletin of Chemical Reaction Engineering and Catalysis, 5(2: 113-126. doi:10.9767/bcrec.5.2.798.113-126][DOI: http://dx.doi.org/10.9767/bcrec.5.2.798.113-126 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/798

  12. CATALYTIC HYDROGENATION AND OXIDATION OF BIOMASS-DERIVED LEVULINIC ACID

    OpenAIRE

    Yan Gong; Lu Lin; Zhipei Yan

    2011-01-01

    Levulinic acid (LA), 4-oxo-pentanoic acid, is a new platform chemical with various potential uses. In this paper, catalytic hydrogenation and oxidation of levulinic acid were studied. It was shown from experiments that levulinic acid can be hydrogenated to γ-valerolactone (GVL) over transition metal catalysts and oxidative-decarboxylated to 2-butanone (methyl-ethyl-ketone, MEK) and methyl-vinyl-ketone (MVK) by cupric oxide (CuO), cupric oxide/cerium oxide (CuO/CeO2), cupric oxide/ alumina (Cu...

  13. Hydrogen-based power generation from bioethanol steam reforming

    International Nuclear Information System (INIS)

    Tasnadi-Asztalos, Zs.; Cormos, C. C.; Agachi, P. S.

    2015-01-01

    This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production from renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO 2 emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint

  14. Hydrogen-based power generation from bioethanol steam reforming

    Energy Technology Data Exchange (ETDEWEB)

    Tasnadi-Asztalos, Zs., E-mail: tazsolt@chem.ubbcluj.ro; Cormos, C. C., E-mail: cormos@chem.ubbcluj.ro; Agachi, P. S. [Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, 11 Arany Janos, Postal code: 400028, Cluj-Napoca (Romania)

    2015-12-23

    This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production from renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO{sub 2} emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint.

  15. Hydrogen-based power generation from bioethanol steam reforming

    Science.gov (United States)

    Tasnadi-Asztalos, Zs.; Cormos, C. C.; Agachi, P. S.

    2015-12-01

    This paper is evaluating two power generation concepts based on hydrogen produced from bioethanol steam reforming at industrial scale without and with carbon capture. The power generation from bioethanol conversion is based on two important steps: hydrogen production from bioethanol catalytic steam reforming and electricity generation using a hydrogen-fuelled gas turbine. As carbon capture method to be assessed in hydrogen-based power generation from bioethanol steam reforming, the gas-liquid absorption using methyl-di-ethanol-amine (MDEA) was used. Bioethanol is a renewable energy carrier mainly produced from biomass fermentation. Steam reforming of bioethanol (SRE) provides a promising method for hydrogen and power production from renewable resources. SRE is performed at high temperatures (e.g. 800-900°C) to reduce the reforming by-products (e.g. ethane, ethene). The power generation from hydrogen was done with M701G2 gas turbine (334 MW net power output). Hydrogen was obtained through catalytic steam reforming of bioethanol without and with carbon capture. For the evaluated plant concepts the following key performance indicators were assessed: fuel consumption, gross and net power outputs, net electrical efficiency, ancillary consumptions, carbon capture rate, specific CO2 emission etc. As the results show, the power generation based on bioethanol conversion has high energy efficiency and low carbon footprint.

  16. Hydrogen mitigation by catalytic recombiners and ignition during severe accidents

    International Nuclear Information System (INIS)

    Rohde, J.; Chakraborty, A.K.; Heitsch, M.; Klein-Hebling, W.

    1994-01-01

    A large amount of hydrogen is expected to be released within a large dry containment of a PWR shortly after the onset of a severe accident, leading to core melting. According to local gas concentrations, turbulence and structural configurations within the containment, the released hydrogen can reach the boundary of deflagration or under certain conditions cause local detonations threatening the containment integrity. During the last few years, several concepts of mitigation have been developed to limit the hydrogen concentrations and extensive efforts have been given to investigate the use of catalytic recombiners as well as the use of deliberate ignition within the contemplated framework of a 'Dual-concept'. Although the recent recommendation of the German Reactor Safety Commission (RSK) foresees the sole application of catalytic recombiners to remove hydrogen during severe accident, a review is planned within two years for the partial and directed additional application of early ignitions or post dilution of the atmosphere of the compartments in conjunction with the recombiners installed. This presentation will review the results of large number of experiments performed both in small scale and large scale to qualify the recombiners. It is also the subject of the presentation to address the requirements for proper and secure functioning of the catalyzers under the existing boundary conditions during the severe accidents. These requirements ask for measures, starting from the proper selection of catalysts, multi purposed catalytic devices and their protection against contamination during the standby condition as well as against aerosol deposition and surface poisoning during the propagation of an accident. A short review of the results to large scale experiments with the combined application of catalytic devices and igniters form also a part of this presentation. (author). 8 refs., 2 tabs., 7 figs

  17. Hydrogen production via catalytic steam reforming of fast pyrolysis oil fractions

    International Nuclear Information System (INIS)

    Wang, D.; Czernik, S.; Montane, D.; Mann, M.; Chornet, E.

    1997-01-01

    Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells, and as a co-adjuvant or autonomous transportation fuel in internal combustion engines. The conversion of biomass to hydrogen can be carried out through two distinct thermochemical strategies: (a) gasification followed by shift conversion; (b) catalytic steam reforming and shift conversion of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper shows that fast pyrolysis of biomass results in a bio-oil that can be adequately fractionated into valuable co-products leaving as by-product an aqueous fraction containing soluble organics (a mixture of alcohols, aldehydes and acids). This fraction can be converted to hydrogen by catalytic steam reforming followed by a shift conversion step. The methods used, the yields obtained and their economic significance will be discussed. (author)

  18. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane

    International Nuclear Information System (INIS)

    Engelmann Pirez, M.

    2004-12-01

    This work deals with the selective catalytic reduction of nitrogen oxides (NO x ), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N 2 , in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO 3 , on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  19. Coal hydrogenation and deashing in ebullated bed catalytic reactor

    Science.gov (United States)

    Huibers, Derk T. A.; Johanson, Edwin S.

    1983-01-01

    An improved process for hydrogenation of coal containing ash with agglomeration and removal of ash from an ebullated bed catalytic reactor to produce deashed hydrocarbon liquid and gas products. In the process, a flowable coal-oil slurry is reacted with hydrogen in an ebullated catalyst bed reaction zone at elevated temperature and pressure conditions. The upward velocity and viscosity of the reactor liquid are controlled so that a substantial portion of the ash released from the coal is agglomerated to form larger particles in the upper portion of the reactor above the catalyst bed, from which the agglomerated ash is separately withdrawn along with adhering reaction zone liquid. The resulting hydrogenated hydrocarbon effluent material product is phase separated to remove vapor fractions, after which any ash remaining in the liquid fraction can be removed to produce substantially ash-free coal-derived liquid products.

  20. Transfer Hydrogenation: Employing a Simple, In Situ Prepared Catalytic System

    KAUST Repository

    Ang, Eleanor Pei Ling

    2017-04-01

    Transfer hydrogenation has been recognized to be an important synthetic method in both academic and industrial research to obtain valuable products including alcohols. Transition metal catalysts based on precious metals, such as Ru, Rh and Ir, are typically employed for this process. In recent years, iron-based catalysts have attracted considerable attention as a greener and more sustainable alternative since iron is earth abundant, inexpensive and non-toxic. In this work, a combination of iron disulfide with chelating bipyridine ligand was found to be effective for the transfer hydrogenation of a variety of ketones to the corresponding alcohols in the presence of a simple base. It provided a convenient and economical way to conduct transfer hydrogenation. A plausible role of sulfide next to the metal center in facilitating the catalytic reaction is demonstrated.

  1. Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

    Science.gov (United States)

    Manzoor, Dar; Pal, Sourav

    2015-06-18

    Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

  2. Catalytic hydrogen peroxide decomposition La1-xSrxCoO3-δ perovskite oxides

    NARCIS (Netherlands)

    Dam, T.V.A.; Olthuis, Wouter; Bergveld, Piet; van den Berg, Albert

    2005-01-01

    Lanthanide perovskite oxides are mentioned as material for hydrogen peroxide sensor because they can catalytically decompose hydrogen peroxide in an aqueous medium. The catalytic properties of these perovskite oxides to hydrogen peroxide are suggested due to their oxygen vacancies influenced by the

  3. Catalytic Dehydrogenation of Ethane in Hydrogen Membrane Reactor

    Science.gov (United States)

    Galuszka, Jan; Giddings, Terry; Clelland, Ian

    The effect of a hydrogen permselective membrane (H-membrane) reactor on catalytic dehydrogenation of ethane was assessed using a fixed bed conventional reactor and a double tubular H-membrane reactor. A 5.0wt.% Cr2O3/γ-Al2O3 catalyst prepared by incipient wetness impregnation of a γ-Al2O3 (BET surface area = 50 m2/g) support was used at 555°C and 600°C. Although about 40% of H2 produced during dehydrogenation of ethane in the membrane reactor passed through the membrane, only moderate enhancement in ethane conversion was observed. The slow processes on the catalyst surface are thought to counterbalance the positive effect of membrane assisted hydrogen removal. Also, decreased selectivity to ethylene due to enhanced carbon formation in the membrane reactor led to faster deactivation of the catalyst. A strategy for commercialization of catalytic dehydrogenation of ethane through the development of a better hydrogen membrane might require a reevaluation.

  4. Catalytic steam reforming of ethanol for hydrogen production: Brief status

    Directory of Open Access Journals (Sweden)

    Bineli Aulus R.R.

    2016-01-01

    Full Text Available Hydrogen represents a promising fuel since it is considered as a cleanest energy carrier and also because during its combustion only water is emitted. It can be produced from different kinds of renewable feedstocks, such as ethanol, in this sense hydrogen could be treated as biofuel. Three chemical reactions can be used to achieve this purpose: the steam reforming (SR, the partial oxidation (POX and the autothermal reforming (ATR. In this study, the catalysts implemented in steam reforming of ethanol were reviewed. A wide variety of elements can be used as catalysts for this reaction, such as base metals (Ni, Cu and Co or noble metals (Rh, Pt and Ru usually deposited on a support material that increases surface area and improves catalytic function. The use of Rh, Ni and Pt supported or promoted with CeO2, and/or La2O3 shows excellent performance in ethanol SR catalytic process. The ratio of water to ethanol, reaction temperatures, catalysts loadings, selectivity and activity are also discussed as they are extremely important for high hydrogen yields.

  5. A low-barrier hydrogen bond mediates antibiotic resistance in a noncanonical catalytic triad

    Science.gov (United States)

    2018-01-01

    One group of enzymes that confer resistance to aminoglycoside antibiotics through covalent modification belongs to the GCN5-related N-acetyltransferase (GNAT) superfamily. We show how a unique GNAT subfamily member uses a previously unidentified noncanonical catalytic triad, consisting of a glutamic acid, a histidine, and the antibiotic substrate itself, which acts as a nucleophile and attacks the acetyl donor molecule. Neutron diffraction studies allow for unambiguous identification of a low-barrier hydrogen bond, predicted in canonical catalytic triads to increase basicity of the histidine. This work highlights the role of this unique catalytic triad in mediating antibiotic resistance while providing new insights into the design of the next generation of aminoglycosides. PMID:29632894

  6. Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

    Directory of Open Access Journals (Sweden)

    Xiaoqing Zhang

    2013-01-01

    Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

  7. Recent advances in catalytic hydrogenation of carbon dioxide.

    Science.gov (United States)

    Wang, Wei; Wang, Shengping; Ma, Xinbin; Gong, Jinlong

    2011-07-01

    Owing to the increasing emissions of carbon dioxide (CO(2)), human life and the ecological environment have been affected by global warming and climate changes. To mitigate the concentration of CO(2) in the atmosphere various strategies have been implemented such as separation, storage, and utilization of CO(2). Although it has been explored for many years, hydrogenation reaction, an important representative among chemical conversions of CO(2), offers challenging opportunities for sustainable development in energy and the environment. Indeed, the hydrogenation of CO(2) not only reduces the increasing CO(2) buildup but also produces fuels and chemicals. In this critical review we discuss recent developments in this area, with emphases on catalytic reactivity, reactor innovation, and reaction mechanism. We also provide an overview regarding the challenges and opportunities for future research in the field (319 references).

  8. Cobaloxime-based photo-catalytic devices for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Fihri, A.; Artero, V.; Razavet, M.; Baffert, C.; Fontecave, M. [CEA Grenoble, DSV, iRTSV, Lab Chim et Biol Metaux, CNRS, UMR 5249, Univ Grenoble 1, F-38054 Grenoble 9 (France); Leibl, W. [CEA, DSV, iBiTecS, Lab Photocatalyse et Biohydrogene, CNRS, URA 2096, Gif Sur Yvette (France)

    2008-07-01

    In this paper is described the synthesis and activity of a series of novel hetero-dinuclear ruthenium-cobaloxime photo-catalysts able to achieve the photochemical production of hydrogen with the highest turnover numbers so far reported for such devices. First of all, substituting cobalt for rare and expensive platinum, palladium, or rhodium metals in photo-catalysts is a first step toward economically viable hydrogen production. Cobaloximes appear to be good candidates for H{sub 2}-evolving catalysts, and they may provide a good basis for the design of photo-catalysts that function in pure water as both the solvent and the sustainable proton source. Secondly, a molecular connection between the sensitizer and the H{sub 2}-evolving catalyst seems to provide advantages regarding the photo-catalytic activity. Structural modifications of this connection should allow a better tuning of the electron transfer between the light-harvesting unit and the catalytic center and thus an increase of the efficiency of the system. (O.M.)

  9. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

    Science.gov (United States)

    Kawasaki, Shin-ichiro; Suzuki, Akira

    2013-01-01

    Summary The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

  10. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

    Directory of Open Access Journals (Sweden)

    Rahat Javaid

    2013-06-01

    Full Text Available The inner surface of a metallic tube (i.d. 0.5 mm was coated with a palladium (Pd-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2 was observed during the reaction, although hydrogen (H2 was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid.

  11. Catalytic Hydrogenation Reaction of Naringin-Chalcone. Study of the Electrochemical Reaction

    Directory of Open Access Journals (Sweden)

    B. A. López de Mishima

    2000-03-01

    Full Text Available The electrocatalytic hydrogenation reaction of naringin derivated chalcone is studied. The reaction is carried out with different catalysts in order to compare with the classic catalytic hydrogenation.

  12. Dealloyed Ruthenium Film Catalysts for Hydrogen Generation from Chemical Hydrides

    Directory of Open Access Journals (Sweden)

    Ramis B. Serin

    2017-07-01

    Full Text Available Thin-film ruthenium (Ru and copper (Cu binary alloys have been prepared on a Teflon™ backing layer by cosputtering of the precious and nonprecious metals, respectively. Alloys were then selectively dealloyed by sulfuric acid as an etchant, and their hydrogen generation catalysts performances were evaluated. Sputtering time and power of Cu atoms have been varied in order to tailor the hydrogen generation performances. Similarly, dealloying time and the sulfuric acid concentration have also been altered to tune the morphologies of the resulted films. A maximum hydrogen generation rate of 35 mL min−1 was achieved when Cu sputtering power and time were 200 W and 60 min and while acid concentration and dealloying time were 18 M and 90 min, respectively. It has also been demonstrated that the Ru content in the alloy after dealloying gradually increased with the increasing the sputtering power of Cu. After 90 min dealloying, the Ru to Cu ratio increased to about 190 times that of bare alloy. This is the key issue for observing higher catalytic activity. Interestingly, we have also presented template-free nanoforest-like structure formation within the context of one-step alloying and dealloying used in this study. Last but not least, the long-time hydrogen generation performances of the catalysts system have also been evaluated along 3600 min. During the first 600 min, the catalytic activity was quite stable, while about 24% of the catalytic activity decayed after 3000 min, which still makes these systems available for the development of robust catalyst systems in the area of hydrogen generation.

  13. Electrocatalytic hydrogenation of organic molecules on conductive new catalytic material

    Energy Technology Data Exchange (ETDEWEB)

    Tountian, D. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide; Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Brisach-Wittmeyer, A.; Menard, H. [Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Nkeng, P.; Poillerat, G. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide

    2008-07-01

    Electrocatalytic hydrogenation (ECH) of organic molecules is a process where chemisorbed hydrogen is produced by electroreduction of water which reacts with the species in bulk. Greater emphasis is being placed on improving the nature of the building material of the electrodes in order to increase ECH efficiency. The effectiveness of the ECH is known to be linked to the nature of electrode materials used and their adsorption properties. This work presented the effect of conductive support material on ECH. The conductive catalysts were obtained from tin dioxide which is chemically stable. Palladium was the catalytic metal used in this study. The production of chemisorbed hydrogen was shown to depend on the quantity of metallic nanoaggregates in electrical contact with the reticulated vitreous carbon use as electrode. The conductive support, F-doped tin dioxide, was obtained by the sol-gel method. The electrocatalysts were characterized by different methods as resistivity measurements, linear sweep voltammetry, XRD, SEM, TGA/DSC, and FTIR analysis. The effects of temperature and time of calcination were also investigated. The study showed that the F-doped SnO2 electrocatalyst appeared to increase the rate of phenol electrohydrogenation. It was concluded that the improved electrocatalytic activity of Pd/F-doped SnO2 can be attributed to the simultaneous polarization of all the metallic Pd nanoaggregates present on the surface as well as in the pores of the matrix by contact with RVC. This results in a better production of chemisorbed atomic hydrogen with a large number of adlienation points. 9 refs., 3 figs.

  14. Noble metal ionic sites for catalytic hydrogen combustion: spectroscopic insights.

    Science.gov (United States)

    Deshpande, Parag A; Madras, Giridhar

    2011-01-14

    A catalytic hydrogen combustion reaction was carried out over noble metal catalysts substituted in ZrO(2) and TiO(2) in ionic form. The catalysts were synthesized by the solution combustion technique. The compounds showed high activity and CO tolerance for the reaction. The activity of Pd and Pt ion substituted TiO(2) was comparable and was higher than Pd and Pt ion substituted ZrO(2). The mechanisms of the reaction over the two supports were proposed by making use of the X-ray photoelectron spectroscopy and FT infrared spectroscopic observations. The reaction over ZrO(2) supported catalysts was proposed to take place by the utilization of the surface hydroxyl groups while the reaction over TiO(2) supported catalysts was hypothesized to be a hybrid mechanism utilizing surface hydroxyl groups and the lattice oxygen.

  15. Hydrogen production from biomass tar by catalytic steam reforming

    International Nuclear Information System (INIS)

    Yoon, Sang Jun; Choi, Young-Chan; Lee, Jae-Goo

    2010-01-01

    The catalytic steam reforming of model biomass tar, toluene being a major component, was performed at various conditions of temperature, steam injection rate, catalyst size, and space time. Two kinds of nickel-based commercial catalyst, the Katalco 46-3Q and the Katalco 46-6Q, were evaluated and compared with dolomite catalyst. Production of hydrogen generally increased with reaction temperature, steam injection rate and space time and decreased with catalyst size. In particular, zirconia-promoted nickel-based catalyst, Katalco 46-6Q, showed a higher tar conversion efficiency and shows 100% conversion even relatively lower temperature conditions of 600 deg. C. Apparent activation energy was estimated to 94 and 57 kJ/mol for dolomite and nickel-based catalyst respectively.

  16. Modelling of the aerosol deposition in a hydrogen catalytic recombiner

    International Nuclear Information System (INIS)

    Vendel, J.; Studer, E.; Zavaleta, P.; Hadida, Ph.

    1997-01-01

    Catalytic recombiners are used to remove the hydrogen released in case of a severe accident in a nuclear power plant, so as to reduce the risk of deflagration or detonation. H 2 PAR experiments are carried out to precise the behaviour of recombiners in term of poisoning by aerosols. Firstly, some calculations have been done with the Trio-EF code to assess the structure of convection loops in the experimental tent. We note that when the recombiner is active, it may have a strong influence on the flow inside the tent and may even interact with an other heat source such as a furnace. In the second part, we study the deposition of aerosols on catalytic plates for a given recombiner, when it is active or passive. We list the different mechanisms and quantify them by introducing the deposition velocity. In fact, thermophoresis appears to be the main mechanism, compared to brownian diffusion or difrusiophoresis, which governs aerosols deposition. It favours deposition on > plates and acts against it for > plates. (author)

  17. Experimental studies on catalytic hydrogen recombiners for light water reactors

    International Nuclear Information System (INIS)

    Drinovac, P.

    2006-01-01

    In the course of core melt accidents in nuclear power plants a large amount of hydrogen can be produced and form an explosive or even detonative gas mixture with aerial oxygen in the reactor building. In the containment atmosphere of pressurized water reactors hydrogen combines a phlogistically with the oxygen present to form water vapor even at room temperature. In the past, experimental work conducted at various facilities has contributed little or nothing to an understanding of the operating principles of catalytic recombiners. Hence, the purpose of the present study was to conduct detailed investigations on a section of a recombiner essentially in order to deepen the understanding of reaction kinetics and heat transport processes. The results of the experiments presented in this dissertation form a large data base of measurements which provides an insight into the processes taking place in recombiners. The reaction-kinetic interpretation of the measured data confirms and deepens the diffusion theory - proposed in an earlier study. Thus it is now possible to validate detailed numeric models representing the processes in recombiners. Consequently the present study serves to broaden and corroborate competence in this significant area of reactor technology. In addition, the empirical knowledge thus gained may be used for a critical reassessment of previous numeric model calculations. (orig.)

  18. Core-shell nanospheres Pt@SiO2 for catalytic hydrogen production

    Science.gov (United States)

    Hu, Yujuan; Wang, Yuqing; Lu, Zhang-Hui; Chen, Xiangshu; Xiong, Lihua

    2015-06-01

    Ultrafine platinum nanoparticles (NPs) embedded in silica nanospheres (Pt@SiO2) have been synthesized in a NP-5/cyclohexane reversed-micelle system followed by NaBH4 reduction. The as-synthesized core-shell nanocatalysts Pt@SiO2 were characterized by scanning electron microscopy, transmission electron microscopes, X-ray powder diffraction analysis, energy dispersive X-ray spectrometer and nitrogen adsorption-desorption investigations. Interestingly, the as-synthesized core-shell nanocatalysts Pt@SiO2 showed an excellent catalytic performance in hydrogen generation from the hydrolysis of ammonia borane (BH3NH3, AB) at room temperature. Especially, the catalytic performance of the Pt@SiO2 remained almost unchanged after the five recycles and even after the heat treatment (673 K), because the silica shells inhibit aggregation or deformation of the metal cores. Besides, the kinetic studies showed that the catalytic hydrolysis of AB was first order with respect to the catalyst concentration and zero order with respect to the substrate concentration, respectively. The excellent catalytic activity and stability of Pt@SiO2 can make it have a bright future in the practical application.

  19. Compact PEM fuel cell system combined with all-in-one hydrogen generator using chemical hydride as a hydrogen source

    International Nuclear Information System (INIS)

    Kim, Jincheol; Kim, Taegyu

    2015-01-01

    Highlights: • Compact fuel cell system was developed for a portable power generator. • Novel concept using an all-in-one reactor for hydrogen generation was proposed. • Catalytic reactor, hydrogen chamber and separator were combined in a volume. • The system can be used to drive fuel cell-powered unmanned autonomous systems. - Abstract: Compact fuel cell system was developed for a portable power generator. The power generator features a polymer electrolyte membrane fuel cell (PEMFC) using a chemical hydride as a hydrogen source. The hydrogen generator extracted hydrogen using a catalytic hydrolysis from a sodium borohydride alkaline solution. A novel concept using an all-in-one reactor was proposed in which a catalyst, hydrogen chamber and byproduct separator were combined in a volume. In addition, the reactor as well as a pump, cooling fans, valves and controller was integrated in a single module. A 100 W PEMFC stack was connected with the hydrogen generator and was evaluated at various load conditions. It was verified that the stable hydrogen supply was achieved and the developed system can be used to drive fuel cell-powered unmanned autonomous systems.

  20. Hypergolic ignition of a catalytically promoted fuel with rocket grade hydrogen peroxide

    Science.gov (United States)

    Pourpoint, Timothee Louis

    significant increase in ignition delay observed with the lowest hydrogen peroxide concentrations. The precise assessment of the relative contribution of heat generation and heat loss due to transport of the ambient gas were difficult to determine in the present experiment. The agreement between the trends and predictions partially substantiate a phenomenological model of hypergolic ignition of a catalytically promoted fuel with rocket grade hydrogen peroxide.

  1. Experimental and Numerical Evaluation of the By-Pass Flow in a Catalytic Plate Reactor for Hydrogen Production

    DEFF Research Database (Denmark)

    Sigurdsson, Haftor Örn; Kær, Søren Knudsen

    2011-01-01

    Numerical and experimental study is performed to evaluate the reactant by-pass flow in a catalytic plate reactor with a coated wire mesh catalyst for steam reforming of methane for hydrogen generation. By-pass of unconverted methane is evaluated under different wire mesh catalyst width to reactor...... duct width ratios, the results show that altering this ratio from 0.98 to 0.96 results in an increase in by-pass mass flow of 22%. Effect of catalytic wire mesh flow resistance on by-pass flow has also been investigated and results show increased by-pass flow as catalytic wire mesh flow resistance...... increases. The numerical results are in good agreement with experimental data. The study improves the understanding of the underlying transport phenomena in these reactors and shows that the flow maldistribution in a catalytic plate reactor using a coated wire mesh has to be considered....

  2. Iron Phthalocyanine as New Efficient Catalyst for Catalytic Transfer Hydrogenation of Simple Aldehydes and Ketones

    Czech Academy of Sciences Publication Activity Database

    Bata, P.; Notheisz, F.; Klusoň, Petr; Zsigmond, A.

    2015-01-01

    Roč. 29, JAN 2015 (2015), s. 45-49 ISSN 0268-2605 Institutional support: RVO:67985858 Keywords : heterogenized complexes * catalytic transfer hydrogenation * reusable catalyst Subject RIV: CC - Organic Chemistry Impact factor: 2.452, year: 2015

  3. Catalytic Response and Stability of Nickel/Alumina for the Hydrogenation of 5-Hydroxymethylfurfural in Water.

    Science.gov (United States)

    Perret, Noémie; Grigoropoulos, Alexios; Zanella, Marco; Manning, Troy D; Claridge, John B; Rosseinsky, Matthew J

    2016-03-08

    The catalytic response of Ni on Al2O3 obtained from Ni-Al layered double hydroxides was studied for the liquid-phase hydrogenation of hydroxymethyl furfural to tetrahydrofuran-2,5-diyldimethanol (THFDM) in water. The successive calcination and reduction of the precursors caused the removal of interlayer hydroxyl and carbonate groups and the reduction of Ni(2+) to Ni(0). Four reduced mixed oxide catalysts were obtained, consisting of different amount of Ni metal contents (47-68 wt%) on an Al-rich amorphous component. The catalytic activity was linked to Ni content whereas selectivity was mainly affected by reaction temperature. THFDM was formed in a stepwise manner at low temperature (353 K) whereas 3-hydroxymethyl cyclopentanone was generated at higher temperature. Coke formation caused deactivation; however, the catalytic activity can be regenerated using heat treatment. The results establish Ni on Al2O3 as a promising catalyst for the production of THFDM in water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Direct catalytic hydrothermal liquefaction of spirulina to biofuels with hydrogen

    Science.gov (United States)

    Zeng, Qin; Liao, Hansheng; Zhou, Shiqin; Li, Qiuping; Wang, Lu; Yu, Zhihao; Jing, Li

    2018-01-01

    We report herein on acquiring biofuels from direct catalytic hydrothermal liquefaction of spirulina. The component of bio-oil from direct catalytic hydrothermal liquefaction was similar to that from two independent processes (including liquefaction and upgrading of biocrude). However, one step process has higher carbon recovery, due to the less loss of carbons. It was demonstrated that the yield and HHV of bio-oil from direct catalytic algae with hydrothermal condition is higher than that from two independent processes.

  5. Effective modeling of hydrogen mixing and catalytic recombination in containment atmosphere with an Eulerian Containment Code

    International Nuclear Information System (INIS)

    Bott, E.; Frepoli, C.; Monti, R.; Notini, V.; Carcassi, M.; Fineschi, F.; Heitsch, M.

    1999-01-01

    Large amounts of hydrogen can be generated in the containment of a nuclear power plant following a postulated accident with significant fuel damage. Different strategies have been proposed and implemented to prevent violent hydrogen combustion. An attractive one aims to eliminate hydrogen without burning processes; it is based on the use of catalytic hydrogen recombiners. This paper describes a simulation methodology which is being developed by Ansaldo, to support the application of the above strategy, in the frame of two projects sponsored by the Commission of the European Communities within the IV Framework Program on Reactor Safety. Involved organizations also include the DCMN of Pisa University (Italy), Battelle Institute and GRS (Germany), Politechnical University of Madrid (Spain). The aims to make available a simulation approach, suitable for use for containment design at industrial level (i.e. with reasonable computer running time) and capable to correctly capture the relevant phenomenologies (e.g. multiflow convective flow patterns, hydrogen, air and steam distribution in the containment atmosphere as determined by containment structures and geometries as well as by heat and mass sources and sinks). Eulerian algorithms provide the capability of three dimensional modelling with a fairly accurate prediction, however lower than CFD codes with a full Navier Stokes formulation. Open linking of an Eulerian code as GOTHIC to a full Navier Stokes CFD code as CFX 4.1 allows to dynamically tune the solving strategies of the Eulerian code itself. The effort in progress is an application of this innovative methodology to detailed hydrogen recombination simulation and a validation of the approach itself by reproducing experimental data. (author)

  6. Automotive dual-mode hydrogen generation system

    Science.gov (United States)

    Kelly, D. A.

    The automotive dual mode hydrogen generation system is advocated as a supplementary hydrogen fuel means along with the current metallic hydride hydrogen storage method for vehicles. This system consists of utilizing conventional electrolysis cells with the low voltage dc electrical power supplied by two electrical generating sources within the vehicle. Since the automobile engine exhaust manifold(s) are presently an untapped useful source of thermal energy, they can be employed as the heat source for a simple heat engine/generator arrangement. The second, and minor electrical generating means consists of multiple, miniature air disk generators which are mounted directly under the vehicle's hood and at other convenient locations within the engine compartment. The air disk generators are revolved at a speed which is proportionate to the vehicles forward speed and do not impose a drag on the vehicles motion.

  7. Hydrogen generation from steam reaction with tungsten

    Science.gov (United States)

    Smolik, G. R.; McCarthy, K. A.; Petti, D. A.; Coates, K.

    1998-10-01

    A LOCA in a fusion reactor involving an ingress of steam presents a safety concern due to hydrogen generated from steam reactions with plasma facing components. Hydrogen concentrations must be maintained below explosive levels. To support safety evaluations we have experimentally determined hydrogen generation rates when a tungsten alloy is exposed to steam from 400°C to 1200°C. We studied effects of steam pressure between 2.8 × 10 4 and 8.5 × 10 4 Pa, i.e., (0.28-0.84 atm) and gas velocity between 0.011 and 0.063 m/s. We present relationships for the reaction rates, oxidation phases, and mechanisms associated with the hydrogen generation.

  8. High temperature solid lubrication by catalytically generated carbon

    Science.gov (United States)

    Lauer, James L.; Bunting, Bruce G.

    1988-01-01

    The wear process in bearings generates a clean active surface. Carbon is known to form readily on catalytic surfaces through the reduction of carbon oxides or hydrocarbon. Carbon, through the adsorption of hydrocarbons, water vapor, or oxygen, becomes an effective lubricant. If these three phenomena can be made to work together, a new concept of high temperature lubrication would be available. This paper presents laboratory investigations towards the development of this concept. Carbon has been successfully produced through catalytic reduction of ethylene on a variety of metallic and ceramic surfaces containing nickel. This carbon has been shown to reduce friction at a sliding interface at elevated temperatures.

  9. Field-controlled electron transfer and reaction kinetics of the biological catalytic system of microperoxidase-11 and hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    Yongki Choi

    2011-12-01

    Full Text Available Controlled reaction kinetics of the bio-catalytic system of microperoxidase-11 and hydrogen peroxide has been achieved using an electrostatic technique. The technique allowed independent control of 1 the thermodynamics of the system using electrochemical setup and 2 the quantum mechanical tunneling at the interface between microperoxidase-11 and the working electrode by applying a gating voltage to the electrode. The cathodic currents of electrodes immobilized with microperoxidase-11 showed a dependence on the gating voltage in the presence of hydrogen peroxide, indicating a controllable reduction reaction. The measured kinetic parameters of the bio-catalytic reduction showed nonlinear dependences on the gating voltage as the result of modified interfacial electron tunnel due to the field induced at the microperoxidase-11-electrode interface. Our results indicate that the kinetics of the reduction of hydrogen peroxide can be controlled by a gating voltage and illustrate the operation of a field-effect bio-catalytic transistor, whose current-generating mechanism is the conversion of hydrogen peroxide to water with the current being controlled by the gating voltage.

  10. Surface spintronics enhanced photo-catalytic hydrogen evolution: Mechanisms, strategies, challenges and future

    Science.gov (United States)

    Zhang, Wenyan; Gao, Wei; Zhang, Xuqiang; Li, Zhen; Lu, Gongxuan

    2018-03-01

    Hydrogen is a green energy carrier with high enthalpy and zero environmental pollution emission characteristics. Photocatalytic hydrogen evolution (HER) is a sustainable and promising way to generate hydrogen. Despite of great achievements in photocatalytic HER research, its efficiency is still limited due to undesirable electron transfer loss, high HER over-potential and low stability of some photocatalysts, which lead to their unsatisfied performance in HER and anti-photocorrosion properties. In recent years, many spintronics works have shown their enhancing effects on photo-catalytic HER. For example, it was reported that spin polarized photo-electrons could result in higher photocurrents and HER turn-over frequency (up to 200%) in photocatalytic system. Two strategies have been developed for electron spin polarizing, which resort to heavy atom effect and magnetic induction respectively. Both theoretical and experimental studies show that controlling spin state of OHrad radicals in photocatalytic reaction can not only decrease OER over-potential (even to 0 eV) of water splitting, but improve stability and charge lifetime of photocatalysts. A convenient strategy have been developed for aligning spin state of OHrad by utilizing chiral molecules to spin filter photo-electrons. By chiral-induced spin filtering, electron polarization can approach to 74%, which is significantly larger than some traditional transition metal devices. Those achievements demonstrate bright future of spintronics in enhancing photocatalytic HER, nevertheless, there is little work systematically reviewing and analysis this topic. This review focuses on recent achievements of spintronics in photocatalytic HER study, and systematically summarizes the related mechanisms and important strategies proposed. Besides, the challenges and developing trends of spintronics enhanced photo-catalytic HER research are discussed, expecting to comprehend and explore such interdisciplinary research in

  11. Nitric-glycolic flowsheet testing for maximum hydrogen generation rate

    Energy Technology Data Exchange (ETDEWEB)

    Martino, C. J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Newell, J. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Williams, M. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-03-01

    The Defense Waste Processing Facility (DWPF) at the Savannah River Site is developing for implementation a flowsheet with a new reductant to replace formic acid. Glycolic acid has been tested over the past several years and found to effectively replace the function of formic acid in the DWPF chemical process. The nitric-glycolic flowsheet reduces mercury, significantly lowers the chemical generation of hydrogen and ammonia, allows purge reduction in the Sludge Receipt and Adjustment Tank (SRAT), stabilizes the pH and chemistry in the SRAT and the Slurry Mix Evaporator (SME), allows for effective adjustment of the SRAT/SME rheology, and is favorable with respect to melter flammability. The objective of this work was to perform DWPF Chemical Process Cell (CPC) testing at conditions that would bound the catalytic hydrogen production for the nitric-glycolic flowsheet.

  12. Production of hydrogen, liquid fuels, and chemicals from catalytic processing of bio-oils

    Science.gov (United States)

    Huber, George W; Vispute, Tushar P; Routray, Kamalakanta

    2014-06-03

    Disclosed herein is a method of generating hydrogen from a bio-oil, comprising hydrogenating a water-soluble fraction of the bio-oil with hydrogen in the presence of a hydrogenation catalyst, and reforming the water-soluble fraction by aqueous-phase reforming in the presence of a reforming catalyst, wherein hydrogen is generated by the reforming, and the amount of hydrogen generated is greater than that consumed by the hydrogenating. The method can further comprise hydrocracking or hydrotreating a lignin fraction of the bio-oil with hydrogen in the presence of a hydrocracking catalyst wherein the lignin fraction of bio-oil is obtained as a water-insoluble fraction from aqueous extraction of bio-oil. The hydrogen used in the hydrogenating and in the hydrocracking or hydrotreating can be generated by reforming the water-soluble fraction of bio-oil.

  13. A new type of hydrogen generator-HHEG (high-compressed hydrogen energy generator)

    International Nuclear Information System (INIS)

    Harada, H.; Tojima, K.; Takeda, M.; Nakazawa, T.

    2004-01-01

    'Full text:' We have developed a new type of hydrogen generator named HHEG (High-compressed Hydrogen Energy Generator). HHEG can produce 35 MPa high-compressed hydrogen for fuel cell vehicle without any mechanical compressor. HHEG is a kind of PEM(proton exchange membrane)electrolysis. It was well known that compressed hydrogen could be generated by water electrolysis. However, the conventional electrolysis could not generate 35 MPa or higher pressure that is required for fuel cell vehicle, because electrolysis cell stack is destroyed in such high pressure. In HHEG, the cell stack is put in high-pressure vessel and the pressure difference of oxygen and hydrogen that is generated by the cell stack is always kept at nearly zero by an automatic compensator invented by Mitsubishi Corporation. The cell stack of HHEG is not so special one, but it is not broken under such high pressure, because the automatic compensator always offsets the force acting on the cell stack. Hydrogen for fuel cell vehicle must be produce by no emission energy such as solar and atomic power. These energies are available as electricity. So, water electrolysis is the only way of producing hydrogen fuel. Hydrogen fuel is also 35 MPa high-compressed hydrogen and will become 70 MPa in near future. But conventional mechanical compressor is not useful for such high pressure hydrogen fuel, because of the short lifetime and high power consumption. Construction of hydrogen station network is indispensable in order to come into wide use of fuel cell vehicles. For such network contraction, an on-site type hydrogen generator is required. HHEG can satisfy above these requirements. So we can conclude that HHEG is the only way of realizing the hydrogen economy. (author)

  14. Basic promoters effect over nickel/alumina catalyst on hydrogen production via methane catalytic partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Requies, J.; Cabrero, M. A.; Barrio, V. I.; Cambra, J. F.; Arias, P. L.; Guemez, B.; La Oarola, V.; Pena, M. A.; Fierro, J. L. G.

    2005-07-01

    The European Directives concerning the environment protection and the sustainable development include the green fuels production and utilization. Thus, one of their major objectives is related to the research on processes to obtain green fuels and their direct application or their transformation in clean energy carriers and final fuels as hydrogen. Hydrogen is an energy vector that is being considered by most countries and many energy companies as a possible long-term solution in the electricity, heating and transport energy markets, where it will offer greenhouse gas abatement and other local air quality benefits. Before the generalization of hydrogen production from renewable resources, other production processes can fulfil the objective of generating an energy infrastructure based on hydrogen. By the methane catalytic partial oxidation (CPO) process or by an analogous one, like Wet CPO, a synthesis gas can be produced. This gas can be further treated to maximize the hydrogen production or it can also be used to generate clean liquid fuels precursors via Fischer-Tropsch synthesis. In the present work, the hydrogen and/or synthesis gas production via CPO or Wet-CPO is studied using nickel catalyst supported on -Al2O3 promoted by basic metals (Ca and Mg). The conventional nickel supported catalysts are highly effective for these processes. Nevertheless, they are unsatisfactory with respect to coke formation. Deactivation of these catalysts by a coke formation is sometimes a serious limitation. The addition of calcium and magnesium onto Ni/ -Al2O3 aims to eliminate the coke formation, via a reduction on support acidity, and as a result to improve these catalysts performance. The catalysts were prepared by consecutive wet impregnation method, and -Al2O3 was employed as acid support. The nominal contents of nickel were 15 and 25 wt%. The nominal contents of promoters were 5 and 10 wt% of Mg or Ca. The catalyst textural characterization was studied using different

  15. The mechanism of the catalytic oxidation of hydrogen sulfide: II. Kinetics and mechanism of hydrogen sulfide oxidation catalyzed by sulfur

    NARCIS (Netherlands)

    Steijns, M.; Derks, F.; Verloop, A.; Mars, P.

    1976-01-01

    The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we

  16. Thermal and catalytic ASVAHL processes under hydrogen pressure for converting heavy crudes and conventional residues

    Energy Technology Data Exchange (ETDEWEB)

    Peries, J.P.; Quignard, A.; Farjon, C.; Laborde, M.

    This article describes the comparative performances of thermal ASVAHL processes (TERVAHL T, TERVAHL H, TERVAHL HC) and catalytic ASVAHL processes (HYVAHL F, HYVAHL C) for two types of processing: (1) degasolined Boscan crude (basis of studies for transportation feasibility), and (2) Safaniya vacuum residue (basis of studies for residue refining). The results reveal the importance of the amount of fixed hydrogen, which affects the conversion obtained and the quality of the residues. The introduction of a TERVAHL HC soluble catalyst or one in catalytic suspension (catalytic hydrovisbreaking) or the use of a supported catalyst (HYVAHL hydrotreatment) enhances the activation of hydrogen. The combination of cracking, polycondensation and hydrogen reactions together with the operating conditions (temperatures, residence time and pressure) are what will define the conversion limits for a given stability of residues.

  17. The ab initio study of the catalytic hydrogenation of the oxirene

    Directory of Open Access Journals (Sweden)

    J.B. Mensah

    2008-04-01

    Full Text Available The oxirene is an unsaturated heterocyclic molecule with one oxygen atom and two carbon atoms. Its hydrogenation has been performed on two catalytic site based on molybdenum disulfide (MoS2 and tungsten disulfide (WS2 of MoS3H3+ and WS3H3+ type, respectively. The calculations were carried out using the SCF and MP2 methods and B3LYP functional calculations. The results obtained showed that the hydrogenation of the oxirene is possible on these two kinds of catalytic sites on the one hand, and the reaction product is the acetaldehyde molecule, on the other hand. The reaction process study that led to the results showed that the catalytic hydrogenation of the oxirene is a dissociative process. On the basis of the variation of some parameters during the process, a mechanism of the reaction has been proposed.

  18. Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

    Directory of Open Access Journals (Sweden)

    Carmen Moreno-Marrodan

    2017-04-01

    Full Text Available The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible.

  19. Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

    Science.gov (United States)

    Moreno-Marrodan, Carmen; Liguori, Francesca

    2017-01-01

    The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible. PMID:28503209

  20. Catalytic on-board hydrogen production from methanol and ammonia for mobile application

    Energy Technology Data Exchange (ETDEWEB)

    Soerijanto, H.

    2008-08-15

    This PhD thesis deals with the catalytic hydrogen production for mobile application, for example for the use in fuel cells for electric cars. Electric powered buses with fuel cells as driving system are well known, but the secure hydrogen storage in adequate amounts for long distance drive is still a topic of discussion. Methanol is an excellent hydrogen carrier. First of all it has a high H:C ratio and therefore a high energy density. Secondly the operating temperature of steam reforming of methanol is comparatively low (250 C) and there is no risk of coking since methanol has no C-C bond. Thirdly methanol is a liquid, which means that the present gasoline infrastructure can be used. For the further development of catalysts and for the construction of a reformer it is very important to characterize the catalysts very well. For the dimensioning and the control of an on-board production of hydrogen it is essential to draw accurately on the thermodynamic, chemical and kinetic data of the reaction. At the first part of this work the mesoporous Cu/ZrO{sub 2}/CeO{sub 2}-catalysts with various copper contents were characterized and their long-term stability and selectivity were investigated, and the kinetic data were determined. Carbon monoxide is generated by reforming of carbon containing material. This process is undesired since CO poisons the Pt electrode of the fuel cell. The separation of hydrogen by metal membranes is technically feasible and a high purity of hydrogen can be obtained. However, due to their high density this procedure is not favourable because of its energy loss. In this study a concept is presented, which enables an autothermal mode by application of ceramic membrane and simultaneously could help to deal with the CO problem. The search for an absolutely selective catalyst is uncertain. The production of CO can be neither chemically nor thermodynamically excluded, if carbon is present in the hydrogen carrier. Since enrichment or separation are

  1. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Hanson, Susan K.; Zhang, Guoqi; Vasudevan, Kalyan V.

    2017-02-14

    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  2. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.

    2016-09-06

    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  3. Model for the simulation of catalytic isotope exchange between tritiated water and hydrogen/deuterium gas

    International Nuclear Information System (INIS)

    Cristescu, Ioana R.; Cristescu, I.; Bornea, Anisia; Penzhorn, R.-D.; Tamm, U.

    2001-01-01

    The objectives of the models presented in this paper are to simulate the deuterium enrichment performances of several catalytic exchange columns under test at the Tritium Laboratory in Karlsruhe (TLK). The models and the corresponding software are presently being verified by experiments aimed to provide the data required for the design of large isotopic exchange columns such as needed for the recovery of tritium from waste water generated during the operation of the tritium facilities of fusion machines. In the ongoing TLK experiments the transfer of deuterium takes place in a counter current isotopic exchange column. Pre-heated water is fed into the column from the top and deuterated hydrogen from the bottom. Condensed water vapor and deuterium-depleted hydrogen are removed from the top and deuterium enriched water from the bottom and analyzed by standard procedures. To describe the performance of the separation process two approaches were considered: a graphical approach (classical) that uses the operating line and equilibrium curve for the process and an analytical approach that solves the transport equations characterizing the isotopic exchange process. (authors)

  4. Partial catalytic oxidation of CH{sub 4} to synthesis gas for power generation - Final report

    Energy Technology Data Exchange (ETDEWEB)

    Mantzaras, I.; Schneider, A.

    2006-03-15

    The partial oxidation of methane to synthesis gas over rhodium catalysts has been investigated experimentally and numerically in the pressure range of 4 to 10 bar. The methane/oxidizer feed has been diluted with large amounts of H{sub 2}O and CO{sub 2} (up to 70% vol.) in order to simulate new power generation cycles with large exhaust gas recycle. Experiments were carried out in an optically accessible channel-flow reactor that facilitated laser-based in situ measurements, and also in a subscale gas-turbine catalytic reactor. Full-elliptic steady and transient two-dimensional numerical codes were used, which included elementary hetero-/homogeneous chemical reaction schemes. The following are the key conclusions: a) Heterogeneous (catalytic) and homogeneous (gas-phase) schemes have been validated for the partial catalytic oxidation of methane with large exhaust gas recycle. b) The impact of added H{sub 2}O and CO{sub 2} has been elucidated. The added H{sub 2}O increased the methane conversion and hydrogen selectivity, while it decreased the CO selectivity. The chemical impact of CO{sub 2} (dry reforming) was minimal. c) The numerical model reproduced the measured catalytic ignition times. It was further shown that the chemical impact of H{sub 2}O and CO{sub 2} on the catalytic ignition delay times was minimal. d) The noble metal dispersion increased with different support materials, in the order Rh/{alpha}-Al{sub 2}O{sub 3}, Rh/ZrO{sub 2}, and Rh/Ce-ZrO{sub 2}. An evident relationship was established between the noble metal dispersion and the catalytic behavior. (authors)

  5. Green Synthesis of (R)-Terbutaline for Recyclable Catalytic Asymmetric Transfer Hydrogenation in Ionic Liquids.

    Science.gov (United States)

    Uchimoto, Hitomi; Ikeda, Miki; Tanida, Saori; Ohhashi, Kayo; Chihara, Yoshiko; Shigeta, Takashi; Arimitsu, Kenji; Yamashita, Masayuki; Nishide, Kiyoharu; Kawasaki, Ikuo

    2017-01-01

    We synthesize optically active (R)-terbutaline 2, which is an anti-asthmatic drug, through recyclable catalytic asymmetric transfer hydrogenation (RCATH). Various chloroketones 4 were prepared and RCATH was performed on them. The products exhibit moderate to high enantioselectivity. In particular, the hydrogenation of acyl substituted substrates 4c yields chiral secondary alcohols 5c in good yield and enantioselectivity. Furthermore, (R)-terbutaline 2 can be synthesized in one step from the resulting secondary alcohol 5 without racemization.

  6. Hydrogen generator characteristics for storage of renewably-generated energy

    International Nuclear Information System (INIS)

    Kotowicz, Janusz; Bartela, Łukasz; Węcel, Daniel; Dubiel, Klaudia

    2017-01-01

    The paper presents a methodology for determining the efficiency of a hydrogen generator taking the power requirements of its auxiliary systems into account. Authors present results of laboratory experiments conducted on a hydrogen generator containing a PEM water electrolyzer for a wide range of device loads. On the basis of measurements, the efficiency characteristics of electrolyzers were determined, including that of an entire hydrogen generator using a monitored power supply for its auxiliary devices. Based on the results of the experimental tests, the authors have proposed generalized characteristics of hydrogen generator efficiency. These characteristics were used for analyses of a Power-to-Gas system cooperating with a 40 MW wind farm with a known yearly power distribution. It was assumed that nightly-produced hydrogen is injected into the natural gas transmission system. An algorithm for determining the thermodynamic and economic characteristics of a Power-to-Gas installation is proposed. These characteristics were determined as a function of the degree of storage of the energy produced in a Renewable Energy Sources (RES) installation, defined as the ratio of the amount of electricity directed to storage to the annual amount of electricity generated in the RES installation. Depending on the degree of storage, several quantities were determined. - Highlights: • The efficiency characteristics of PEM electrolyzer are determined. • Generalized characteristics of hydrogen generator efficiency are proposed. • Method of choice of electrolyser nominal power for Power-to-Gas system was proposed. • Development of Power-to-Gas systems requires implementation of support mechanisms.

  7. Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions.

    Science.gov (United States)

    Li, Gao; Abroshan, Hadi; Chen, Yuxiang; Jin, Rongchao; Kim, Hyung J

    2015-11-18

    The catalytic activity of Au25(SR)18 nanoclusters (R = C2H4Ph) for the aldehyde hydrogenation reaction in the presence of a base, e.g., ammonia or pyridine, and transition-metal ions M(z+), such as Cu(+), Cu(2+), Ni(2+) and Co(2+), as a Lewis acid is studied. The addition of a Lewis acid is found to significantly promote the catalytic activity of Au25(SR)18/CeO2 in the hydrogenation of benzaldehyde and a number of its derivatives. Matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry in conjunction with UV-vis spectroscopy confirm the generation of new species, Au25-n(SR)18-n (n = 1-4), in the presence of a Lewis acid. The pathways for the speciation of Au24(SR)17 from its parent Au25(SR)18 nanocluster as well as its structure are investigated via the density functional theory (DFT) method. The adsorption of M(z+) onto a thiolate ligand "-SR-" of Au25(SR)18, followed by a stepwise detachment of "-SR-" and a gold atom bonded to "-SR-" (thus an "Au-SR" unit) is found to be the most likely mechanism for the Au24(SR)17 generation. This in turn exposes the Au13-core of Au24(SR)17 to reactants, providing an active site for the catalytic hydrogenation. DFT calculations indicate that M(z+) is also capable of adsorbing onto the Au13-core surface, producing a possible active metal site of a different kind to catalyze the aldehyde hydrogenation reaction. This study suggests, for the first time, that species with an open metal site like adducts [nanoparticle-M]((z-1)+) or fragments Au25-n(SR)18-n function as the catalysts rather than the intact Au25(SR)18.

  8. Hydrogen production by aqueous phase catalytic reforming of glycerine

    International Nuclear Information System (INIS)

    Ozguer, Derya Oncel; Uysal, Bekir Zuehtue

    2011-01-01

    Hydrogen is believed to be the one of the main energy carriers in the near future. In this research glycerine, which is produced in large quantities as a by-product of biodiesel process, was converted to hydrogen aiming to contribute to clean energy initiative. Conversion of glycerol to hydrogen was achieved via aqueous-phase reforming (APR) with Pt/Al 2 O 3 catalyst. The experiments were carried out in an autoclave reactor and a continuous fixed-bed reactor. The effects of reaction temperature (160-280 o C), feed flow rate (0.05-0.5 mL/dak) and feed concentration (5-85 wt-% glycerine) on product distribution were investigated. Optimum temperature for hydrogen production with APR was determined as 230 o C. Maximum gas production rate was found at the feed flow rates around 0.1 mL/min. It was also found that hydrogen concentration in the gas product increased with decreasing glycerol concentration in the feed.

  9. Low temperature catalytic reforming of heptane to hydrogen and syngas

    Directory of Open Access Journals (Sweden)

    M.E.E. Abashar

    2016-09-01

    Full Text Available The production of hydrogen and syngas from heptane at a low temperature is studied in a circulating fast fluidized bed membrane reactor (CFFBMR. A thin film of palladium-based membrane is employed to the displacement of the thermodynamic equilibrium for high conversion and yield. A mathematical model is developed to simulate the reformer. A substantial improvement of the CFFBMR is achieved by implementing the thin hydrogen membrane. The results showed that almost complete conversion of heptane and 46.25% increase of exit hydrogen yield over the value without membrane are achieved. Also a wide range of the H2/CO ratio within the recommended industrial range is obtained. The phenomena of high spikes of maximum nature at the beginning of the CFFBMR are observed and explanation offered. The sensitivity analysis results have shown that the increase of the steam to carbon feed ratio can increase the exit hydrogen yield up to 108.29%. It was found that the increase of reaction side pressure at a high steam to carbon feed ratio can increase further the exit hydrogen yield by 49.36% at a shorter reactor length. Moreover, the increase of reaction side pressure has an important impact in a significant decrease of the carbon dioxide and this is a positive sign for clean environment.

  10. Catalytic hydrogenation of carbon dioxide using Ir(III)-pincer complexes.

    Science.gov (United States)

    Tanaka, Ryo; Yamashita, Makoto; Nozaki, Kyoko

    2009-10-14

    Catalytic hydrogenation of carbon dioxide in aqueous potassium hydroxide was performed using a newly synthesized isopropyl-substituted PNP-pincer iridium trihydride complex as a catalyst. Potassium formate was obtained with turnover numbers up to 3,500,000 and a turnover frequency of 150,000 h(-1), both of which are the highest values reported to date.

  11. Ultrathin Alumina Mask-Assisted Nanopore Patterning on Monolayer MoS2 for Highly Catalytic Efficiency in Hydrogen Evolution Reaction.

    Science.gov (United States)

    Su, Shaoqiang; Zhou, Qingwei; Zeng, Zhiqiang; Hu, Die; Wang, Xin; Jin, Mingliang; Gao, Xingsen; Nötzel, Richard; Zhou, Guofu; Zhang, Zhang; Liu, Junming

    2018-03-07

    Nanostructured molybdenum disulfide (MoS 2 ) has been considered as one of the most promising catalysts in the hydrogen evolution reaction (HER), for its approximately intermediate hydrogen binding free energy to noble metals and much lower cost. The catalytically active sites of MoS 2 are along the edges, whereas thermodynamically MoS 2 favors the presence of a two-dimensional (2-D) basal plane and the catalytically active atoms only constitute a small portion of the material. The lack of catalytically active sites and low catalytic efficiency impede its massive application. To address the issue, we have activated the basal plane of monolayer 2H MoS 2 through an ultrathin alumina mask (UTAM)-assisted nanopore arrays patterning, creating a high edge density. The introduced catalytically active sites are identified by Cu electrochemical deposition, and the hydrogen generation properties are assessed in detail. We demonstrate a remarkably improved HER performance as well as the identical catalysis of the artificial edges and the pristine metallic edges of monolayer MoS 2 . Such a porous monolayer nanostructure can achieve a much higher edge atom ratio than the pristine monolayer MoS 2 flakes, which can lead to a much improved catalytic efficiency. This controllable edge engineering can also be extended to the basal plane modifications of other 2-D materials, for improving their edge-related properties.

  12. Hydrogen Production From catalytic reforming of greenhouse gases ...

    African Journals Online (AJOL)

    Hydrogen production from CO2 reforming of methane over 20wt%.Co/Nd2O3 has been investigated in a fixed bed stainless steel reactor. The 20wt%.Co/Nd2O3 catalyst was synthesized using wet impregnation method and characterized for thermal stability, textural property, crystallinity, morphology and nature of chemical ...

  13. Catalytic Metal Free Production of Large Cage Structure Carbon Particles: A Candidate for Hydrogen Storage

    Science.gov (United States)

    Kimura, Yuki; Nuth, Joseph A., III; Ferguson, Frank T.

    2005-01-01

    We will demonstrate that carbon particles consisting of large cages can be produced without catalytic metal. The carbon particles were produced in CO gas as well as by introduction of 5% methane gas into the CO gas. The gas-produced carbon particles were able to absorb approximately 16.2 wt% of hydrogen. This value is 2.5 times higher than the 6.5 wt% goal for the vehicular hydrogen storage proposed by the Department of Energy in the USA. Therefore, we believe that this carbon particle is an excellent candidate for hydrogen storage for fuel cells.

  14. Low temperature catalytic combustion of natural gas - hydrogen - air mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Newson, E.; Roth, F. von; Hottinger, P.; Truong, T.B. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The low temperature catalytic combustion of natural gas - air mixtures would allow the development of no-NO{sub x} burners for heating and power applications. Using commercially available catalysts, the room temperature ignition of methane-propane-air mixtures has been shown in laboratory reactors with combustion efficiencies over 95% and maximum temperatures less than 700{sup o}C. After a 500 hour stability test, severe deactivation of both methane and propane oxidation functions was observed. In cooperation with industrial partners, scaleup to 3 kW is being investigated together with startup dynamics and catalyst stability. (author) 3 figs., 3 refs.

  15. Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS{sub 2} layers

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, R. K., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in; Sahajwalla, V. [Centre for Sustainable Materials Research and Technology, School of Materials Science and Engineering, University of New South Wales, NSW 2052 (Australia); Shukla, S.; Saxena, S. [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai (India); Lee, G.-H. [Department of Material Science and Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of); Alwarappan, S., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in [CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India)

    2016-01-15

    Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS{sub 2}, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS{sub 2} layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS{sub 2} film resulted in hydrogen evolution. Our work shows that 2D MoS{sub 2} is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS{sub 2} shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS{sub 2} is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.

  16. Molecular catalytic hydrogenation of aromatic hydrocarbons and hydrotreating of coal liquids.

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Shiyong; Stock, L.M.

    1996-05-01

    This report presents the results of research on the development of new catalytic pathways for the hydrogenation of multiring aromatic hydrocarbons and the hydrotreating of coal liquids at The University of Chicago under DOE Contract No. DE-AC22-91PC91056. The work, which is described in three parts, is primarily concerned with the research on the development of new catalytic systems for the hydrogenation of aromatic hydrocarbons and for the improvement of the quality of coal liquids by the addition of dihydrogen. Part A discusses the activation of dihydrogen by very basic molecular reagents to form adducts that can facilitate the reduction of multiring aromatic hydrocarbons. Part B examines the hydrotreating of coal liquids catalyzed by the same base-activated dihydrogen complexes. Part C concerns studies of molecular organometallic catalysts for the hydrogenation of monocyclic aromatic hydrocarbons under mild conditions.

  17. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

    Science.gov (United States)

    Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

    2018-01-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994

  18. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

    Directory of Open Access Journals (Sweden)

    Qiang Lu

    2018-02-01

    Full Text Available A new technique was proposed to co-produce phenol and activated carbon (AC from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g.

  19. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

    Science.gov (United States)

    Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping

    2018-01-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.

  20. CATALYTICALLY ENHANCED SYSTEMS FOR HYDROGEN STORAGE. Final report

    International Nuclear Information System (INIS)

    Craig M. Jensen

    2007-01-01

    Previous U.S. DOE sponsored research at the University of Hawaii resulted in the development of methods of doping of sodium aluminum hydride, NaAlH4 with titanium, zirconium and other catalysts such that: dehydriding occurs at temperatures as low as 100 C; rehydriding requires less than 1 h; and >4 weight percent hydrogen can be repeatedly cycled through dehydriding/rehydriding. These materials appeared to be on the threshold of practical viability as hydrogen carriers for onboard fuel cells. However, it was apparent that further kinetic enhancement was required to achieve commercial viability. Thus, one of the primary goals of this project was to develop the requisite improved catalysts. Over the course of this project, a variety of titanium and zirconium dopant precursors were investigated. Moreover, the approach was to conduct guided search for improved catalysts by obtaining a fundamental understanding of the chemical nature of the titanium dopants and their mechanism of action. Therefore, the projected also aimed to determined the chemical nature of the titanium species that are formed upon mechanical milling of NaAlH4 with the dopant precursors through synchrotron X-ray and neutron diffraction as well as transmission electron microscopy, scanning electron microscopy, and electron paramagnetic resonance (EPR) spectroscopy. In addition to kinetic studies, insight into the mechanism of action of the dopants was gained through studies of the destabilization of hydrogen in NaAlH4 by the dopants through infrared, NMR, and anelastic spectroscopy

  1. Catalytic Hydrogenation of Bio-Oil for Chemicals and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.

    2006-02-14

    The scope of work includes optimizing processing conditions and demonstrating catalyst lifetime for catalyst formulations that are readily scaleable to commercial operations. We use a bench-scale, continuous-flow, packed-bed, catalytic, tubular reactor, which can be operated in the range of 100-400 mL/hr., from 50-400 C and up to 20MPa (see Figure 1). With this unit we produce upgraded bio-oil from whole bio-oil or useful bio-oil fractions, specifically pyrolytic lignin. The product oils are fractionated, for example by distillation, for recovery of chemical product streams. Other products from our tests have been used in further testing in petroleum refining technology at UOP and fractionation for product recovery in our own lab. Further scale-up of the technology is envisioned and we will carry out or support process design efforts with industrial partners, such as UOP.

  2. Production of hydrogen from bio-ethanol in catalytic membrane reactor

    International Nuclear Information System (INIS)

    Gernot, E.; Aupretre, F.; Deschamps, A.; Etievant, C.; Epron, F.; Marecot, P.; Duprez, D.

    2006-01-01

    Production of hydrogen from renewable energy sources offers a great potential for CO 2 emission reduction, responsible for global warming. Among renewable energies, liquid biofuels are very convenient hydrogen carriers for decentralized applications such as micro-cogeneration and transports. Ethanol, produced from sugar plants and cereals, allows a reduction of more than 60% of CO 2 emissions in comparison to gasoline. BIOSTAR is an R and D project, co-funded by the French Agency for Environment and Energy Management (ADEME) which aims at developing an efficient source of hydrogen from bio-ethanol, suitable for proton exchange membrane fuel cell systems. The objectives are to obtain, through catalytic process at medium temperature range, an efficient conversion of bio-ethanol into pure hydrogen directly usable for PEMFC. CETH has developed a catalytic membrane reformer (CMR), based on a patented technology, integrating a steam reforming catalyst as well as a combustion catalyst. Both catalysts have been developed and optimized for membrane reactor in partnership with the University of Poitiers. The composite metallic membrane developed by CETH allows hydrogen extraction near the hydrogen production sites, which enhances both efficiency and compactness. (authors)

  3. Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yaping [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States); Liu, Zhimin [School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019 (United States); Xue, Wenhua [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States); Crossley, Steven P.; Jentoft, Friederike C. [School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK 73019 (United States); Wang, Sanwu, E-mail: sanwu-wang@utulsa.edu [Department of Physics and Engineering Physics, The University of Tulsa, Tulsa, OK 74104 (United States)

    2017-01-30

    Highlights: • Hydrogenation of o-cresol over Pt results in formation of two products. • Dissociation of hydrogen from the −OH group involves a low activation energy. • Following hydrogenation of the aromatic ring forms 2-methyl-cyclohexanone. • Further hydrogenation produces the final product, 2-methyl-cyclohexanol. - Abstract: Catalytic experiments were performed for the hydrogenation of o-cresol in n-dodecane over a platinum catalyst. Batch reactions analyzed with an in-situ ATR IR probe suggest that the hydrogenation results in the formation of the final product, 2-methyl-cyclohexanol, with 2-methyl-cyclohexanone as the intermediate product. Ab initio density-functional theory was employed to investigate the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone was found to involve two steps. The first step is a hydrogen abstraction, that is, the H atom in the hydroxyl group migrates to the Pt surface. The second step is hydrogenation, that is, the pre-existing H atoms on Pt react with the carbon atoms in the aromatic ring. On the other hand, 2-methyl-cyclohexanonol may be produced through two paths, with activation energies slightly greater than that for the formation of 2-methyl-cyclohexanone. One path involves direct hydrogenation of the aromatic ring. Another path involves three steps, with the partial hydrogenation of the ring as the first step, hydrogen abstraction of the −OH group as the second, and hydrogenation of remaining C atoms and the O atom the last.

  4. Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

    International Nuclear Information System (INIS)

    Li, Yaping; Liu, Zhimin; Xue, Wenhua; Crossley, Steven P.; Jentoft, Friederike C.; Wang, Sanwu

    2017-01-01

    Highlights: • Hydrogenation of o-cresol over Pt results in formation of two products. • Dissociation of hydrogen from the −OH group involves a low activation energy. • Following hydrogenation of the aromatic ring forms 2-methyl-cyclohexanone. • Further hydrogenation produces the final product, 2-methyl-cyclohexanol. - Abstract: Catalytic experiments were performed for the hydrogenation of o-cresol in n-dodecane over a platinum catalyst. Batch reactions analyzed with an in-situ ATR IR probe suggest that the hydrogenation results in the formation of the final product, 2-methyl-cyclohexanol, with 2-methyl-cyclohexanone as the intermediate product. Ab initio density-functional theory was employed to investigate the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone was found to involve two steps. The first step is a hydrogen abstraction, that is, the H atom in the hydroxyl group migrates to the Pt surface. The second step is hydrogenation, that is, the pre-existing H atoms on Pt react with the carbon atoms in the aromatic ring. On the other hand, 2-methyl-cyclohexanonol may be produced through two paths, with activation energies slightly greater than that for the formation of 2-methyl-cyclohexanone. One path involves direct hydrogenation of the aromatic ring. Another path involves three steps, with the partial hydrogenation of the ring as the first step, hydrogen abstraction of the −OH group as the second, and hydrogenation of remaining C atoms and the O atom the last.

  5. Hanford Waste Vitrification Plant hydrogen generation

    International Nuclear Information System (INIS)

    King, R.B.; King, A.D. Jr.; Bhattacharyya, N.K.

    1996-02-01

    The most promising method for the disposal of highly radioactive nuclear wastes is a vitrification process in which the wastes are incorporated into borosilicate glass logs, the logs are sealed into welded stainless steel canisters, and the canisters are buried in suitably protected burial sites for disposal. The purpose of the research supported by the Hanford Waste Vitrification Plant (HWVP) project of the Department of Energy through Battelle Pacific Northwest Laboratory (PNL) and summarized in this report was to gain a basic understanding of the hydrogen generation process and to predict the rate and amount of hydrogen generation during the treatment of HWVP feed simulants with formic acid. The objectives of the study were to determine the key feed components and process variables which enhance or inhibit the.production of hydrogen. Information on the kinetics and stoichiometry of relevant formic acid reactions were sought to provide a basis for viable mechanistic proposals. The chemical reactions were characterized through the production and consumption of the key gaseous products such as H 2 . CO 2 , N 2 0, NO, and NH 3 . For this mason this research program relied heavily on analyses of the gases produced and consumed during reactions of the HWVP feed simulants with formic acid under various conditions. Such analyses, used gas chromatographic equipment and expertise at the University of Georgia for the separation and determination of H 2 , CO, CO 2 , N 2 , N 2 O and NO

  6. Metal dependent catalytic hydrogenation of nitroarenes over water-soluble glutathione capped metal nanoparticles.

    Science.gov (United States)

    Sharma, Sachil

    2015-03-01

    The water soluble glutathione capped metal nanoparticles (M-GS, where M=Pd, Pt, Au and Ag; GS=glutathione) with size 2.4±0.2 nm were synthesized by borohydride reduction of metal ions in the presence of glutathione as capping ligand and used as catalyst for the hydrogenation of nitroaniline in aqueous phase. The rate of catalytic hydrogenation was dependent on metal type and the trend of catalytic activity over these M-GS nanoparticles was found to be Pd-GS (k(app)=0.0227 (±3×10(-4)))s(-1)≫Pt-GS (k(app)=0.0043 (±1×10(-4)))s(-1)>Au-GS (k(app)=0.0015 (±0.2×10(-4)))s(-1)>Ag-GS (k(app)=0.0008 (±0.2×10(-4)))s(-1). The similar trend of catalytic activity was found for the hydrogenation of nitrobenzene. Our experimental results, along taking into account the theoretical calculations done by other research groups, suggest that the observed catalytic activity trend is attributed to the "different rates of H2 molecule adsorption and dissociation" on the M-GS nanoparticles. The "high rate of H2 molecule adsorption" and "highly oxidized surface" make Pd-GS nanoparticles an ideal candidate for the rapid hydrogenation. On the basis of our experimental results, we proposed that small gaps between less densely packed branched thiol "glutathione molecules" provide the access to metal nanoparticle surface for the hydrogenation reaction. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. [Non-nascent hydrogen mechanism of plumbane generation].

    Science.gov (United States)

    Zou, Yan; Jin, Fu-xia; Chen, Zhi-jiang; Qiu, De-ren; Yang, Peng-yuan

    2005-10-01

    The mechanism of plumbane generation in dichromate system was studied via investigation of the relationship between the plumbane yield and the molar number of the reactants. A flow injection hydride generator was used in the study. Reactant moler number was calculated by the injected volume and the reactant concentration, and the plumbane yield was measured via an AAS spectrometer equipped with an electrothermal quartz tube atomizer. Experimental results show that the acid was first used for the neutralization of NaOH and successively participated in the redox reaction of borohydride with dichromate with a constant molar ratio of 9.95 +/- 0.42 (expressed in terms of mean +/- standard deviation). At the same time, plumbane generation was displayed as synchronously taking place with the redox reaction, and the yield increased with the increase of acid. The mechanism of plumbane generation was thus deduced as an induced reaction or a catalytic reaction by the redox reaction. Up to this end, the non-nascent hydrogen mechanism of hydride generation has been verified for all the IVA elements.

  8. Electroless Nickel-Based Catalyst for Diffusion Limited Hydrogen Generation through Hydrolysis of Borohydride

    Directory of Open Access Journals (Sweden)

    Shannon P. Anderson

    2013-07-01

    Full Text Available Catalysts based on electroless nickel and bi-metallic nickel-molybdenum nanoparticles were synthesized for the hydrolysis of sodium borohydride for hydrogen generation. The catalysts were synthesized by polymer-stabilized Pd nanoparticle-catalyzation and activation of Al2O3 substrate and electroless Ni or Ni-Mo plating of the substrate for selected time lengths. Catalytic activity of the synthesized catalysts was tested for the hydrolyzation of alkaline-stabilized NaBH4 solution for hydrogen generation. The effects of electroless plating time lengths, temperature and NaBH4 concentration on hydrogen generation rates were analyzed and discussed. Compositional analysis and surface morphology were carried out for nano-metallized Al2O3 using Scanning Electron Micrographs (SEM and Energy Dispersive X-Ray Microanalysis (EDAX. The as-plated polymer-stabilized electroless nickel catalyst plated for 10 min and unstirred in the hydrolysis reaction exhibited appreciable catalytic activity for hydrolysis of NaBH4. For a zero-order reaction assumption, activation energy of hydrogen generation using the catalyst was estimated at 104.6 kJ/mol. Suggestions are provided for further work needed prior to using the catalyst for portable hydrogen generation from aqueous alkaline-stabilized NaBH4 solution for fuel cells.

  9. Hydrogen assisted catalytic biomass pyrolysis. Effect of temperature and pressure

    DEFF Research Database (Denmark)

    Stummann, M.Z.; Høj, M.; Schandel, C. B.

    2018-01-01

    . The effect of varying the temperature (365–511 °C) and hydrogen pressure (1.6–3.6 MPa) on the product yield and organic composition was studied. The mass balance closed by a mass fraction between 90 and 101% dry ash free basis (daf). The yield of the combined condensed organics and C4+ varied between a mass...... fraction of 17 and 22% daf, corresponding to an energy recovery of between 40 and 53% in the organic product. The yield of the non-condensable gases varied between a mass fraction of 24 and 32% daf and the char yield varied between 9.6 and 18% daf. The condensed organics contained a mass fraction of 42...

  10. Volatility of the catalytic hydrogenation products of 1,4 bis(phenylethynyl)benzene

    Science.gov (United States)

    Sharma, Hom N.; Sangalang, Elizabeth A.; Saw, Cheng K.; Cairns, Gareth A.; McLean, William; Maxwell, Robert S.; Dinh, Long N.

    2017-11-01

    Measurements of equilibrium vapor pressures by effusion thermogravimetry and melting points by differential scanning calorimetry reveal that the melting temperature and equilibrium vapor pressures of 1,4-bis(phenylethynyl)benzene (DEB) do not vary monotonically with the hydrogenation extent. Contrary to intuition which suggests increasing volatility with hydrogenation, results indicate decreasing volatility for the first two hydrogenation steps before a non-monotonic upward trend, in which trans-isomers are less volatile. Insights on structural packing and functional groups were obtained from x-ray diffraction and infrared studies to shed light on the observed variation in the volatility of DEB with hydrogenation. Density functional theory calculations were performed to obtain molecular level information and to establish the thermodynamics of DEB hydrogenation reactions. A major factor influencing the observed melting points and volatility of the hydrogenated intermediate species is identified as the local attractive or repulsive carbon-hydrogen (CH) dipole interactions among the getter molecules in their respective crystal structures. Such collective CH dipole interactions can be used to predict the trends in the volatilities of catalytic hydrogenation processes.

  11. [Noncompetitive immunochemical determination of ribonuclease using transition metal ions and the effect of catalytic hydrogen release].

    Science.gov (United States)

    Dykhal, Iu I; Mediantseva, E P; Murtazina, N R; Safina, G R; Budnikov, G K; Kalacheva, N V

    2003-01-01

    A noncompetitive variant of immunochemical ribonuclease (RNase) determination has been developed, involving the use of Co(II) as a label. A variety of approaches to labeling the immunological reagent with the metal have been assessed. In the variant proposed, catalytic hydrogen release was used as a means of detecting the label, the amount of which was proportional to RNase concentration. Conditions making it possible to record catalytic hydrogen release fluxes were determined. In the presence of RNase, the electrocatalytic effect was maximum at a concentration of Co(II) in the ammoniac buffer, equal to 2 x 10(-4) M (pH 10.0). The dependence was linear in the range 4-2000 ng/ml RNase concentrations (threshold concentration, 2 ng/ml).

  12. A new type separation column for the water-hydrogen isotope catalytic exchange process

    International Nuclear Information System (INIS)

    Fedorchenko, O.A.; Alekseev, I.A.; Trenin, V.D.

    2001-01-01

    The catalytic water/hydrogen isotope exchange process is by right considered the most attractive for the solution a number of urgent problems of hydrogen isotope separation. A new type exchange reaction column is described and studied in details by computer simulation and with the help of McCabe-Thiele diagrams. It is shown that the new column in comparison with a traditional one needs less catalyst quantity and a smaller diameter for the solving of the same separation tasks. Generalized calculation data are presented in graphical form

  13. Composite mixed ion-electron conducting (MIEC) membranes for hydrogen generation and separation

    Science.gov (United States)

    Wang, Haibing

    Decomposition of steam under a chemical driving force at moderate temperatures (˜900°C) offers a convenient and economical way to generate hydrogen. A significant amount of hydrogen can be generated and separated by splitting steam and removing oxygen using a mixed ion-electron conducting (MIEC) membrane. In this work, Gd0.2Ce0.8O1.9-deltaGd 0.08Sr0.88Ti0.95Al0.05O3+/-delta MIEC membranes have been explored in which, Gd0.2Ce 0.8O1.9-delta (GDC) functions as a predominantly oxygen ionic conductor, and Gd0.08Sr0.88Ti0.95Al 0.05O3+/-delta (GSTA) functions as a predominantly n-type electronic conductor under the process conditions. During the hydrogen generation process, oxygen transports from the feed side to the permeate side through coupled diffusion of oxygen ions and electrons under an oxygen partial pressure gradient across membranes. This process results in a H2-rich product on the feed side and depleted fuel gases on the permeate side. In this work, membrane architectures comprising self-supported thick membranes and thin membranes supported on porous supports of the same composition have been studied. The effect of membrane thickness on hydrogen generation has been studied by measuring the area-specific hydrogen generation rates at different experimental conditions. Experimental results have shown that the hydrogen generation process for the thick membranes was controlled by the oxygen bulk diffusion through membranes, while the hydrogen generation process for the dense thin membranes was controlled by both the surface exchange reactions and oxygen bulk diffusion process. The area-specific hydrogen generation rates of the supported dense thin membranes were significantly enhanced by applying a porous catalytic layer onto the surface of the membrane. Experimental results showed that the area-specific hydrogen generation rates were higher when the surface catalytic layer was exposed to the feed side rather than the permeate side. A mathematical model for

  14. State of the art on hydrogen passive auto-catalytic recombiner (european union Parsoar project)

    International Nuclear Information System (INIS)

    Arnould, F.; Bachellerie, E.; Auglaire, M.; Boeck, B. de; Braillard, O.; Eckardt, B.; Ferroni, F.; Moffett, R.; Van Goethem, G.

    2001-01-01

    This paper presents an overview of the European Union PARSOAR project, which consists in carrying out a state of the art on hydrogen passive auto-catalytic recombiner (PAR) and a handbook guide for implementing these devices in nuclear power plants. This work is performed in the area ''Operational Safety of Existing Installations'' of the key action ''Nuclear Fission'' of the fifth Euratom Framework Programme (1998-2002). (author)

  15. State of the art on hydrogen passive auto-catalytic recombiner (european union Parsoar project)

    Energy Technology Data Exchange (ETDEWEB)

    Arnould, F.; Bachellerie, E. [Technicatome, 13 - Aix en Provence (France); Auglaire, M. [Tractebel Energy Engineering, Brussels (Belgium); Boeck, B. de [Association Vincotte Nuclear, Brussels (Belgium); Braillard, O. [CEA Cadarache, 13 - Saint Paul lez Durance (France); Eckardt, B. [Siemens AG, Offenbach am Main (Germany); Ferroni, F. [Electrowatt Engineering Limited, Zurich (Switzerland); Moffett, R. [Atomic Energy Canada Limited, Pinawa (Canada); Van Goethem, G. [European Commission, Brussels (Belgium)

    2001-07-01

    This paper presents an overview of the European Union PARSOAR project, which consists in carrying out a state of the art on hydrogen passive auto-catalytic recombiner (PAR) and a handbook guide for implementing these devices in nuclear power plants. This work is performed in the area ''Operational Safety of Existing Installations'' of the key action ''Nuclear Fission'' of the fifth Euratom Framework Programme (1998-2002). (author)

  16. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion.

    Science.gov (United States)

    Tanabe, Katsuaki

    2016-01-01

    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  17. Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts.

    Science.gov (United States)

    Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G

    2015-06-22

    The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A hydrogen-bonding network plays a catalytic role in photosynthetic oxygen evolution

    Science.gov (United States)

    Polander, Brandon C.; Barry, Bridgette A.

    2012-01-01

    In photosystem II, oxygen evolution occurs by the accumulation of photo-induced oxidizing equivalents at the oxygen-evolving complex (OEC). The sequentially oxidized states are called the S0-S4 states, and the dark stable state is S1. Hydrogen bonds to water form a network around the OEC; this network is predicted to involve multiple peptide carbonyl groups. In this work, we tested the idea that a network of hydrogen bonded water molecules plays a catalytic role in water oxidation. As probes, we used OEC peptide carbonyl frequencies, the substrate-based inhibitor, ammonia, and the sugar, trehalose. Reaction-induced FT-IR spectroscopy was used to describe the protein dynamics associated with the S1 to S2 transition. A shift in an amide CO vibrational frequency (1664 (S1) to 1653 (S2) cm-1) was observed, consistent with an increase in hydrogen bond strength when the OEC is oxidized. Treatment with ammonia/ammonium altered these CO vibrational frequencies. The ammonia-induced spectral changes are attributed to alterations in hydrogen bonding, when ammonia/ammonium is incorporated into the OEC hydrogen bond network. The ammonia-induced changes in CO frequency were reversed or blocked when trehalose was substituted for sucrose. This trehalose effect is attributed to a displacement of ammonia molecules from the hydrogen bond network. These results imply that ammonia, and by extension water, participate in a catalytically essential hydrogen bond network, which involves OEC peptide CO groups. Comparison to the ammonia transporter, AmtB, reveals structural similarities with the bound water network in the OEC. PMID:22474345

  19. Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation.

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Wenyu; Kuhn, John N.; Tsung, Chia-Kuang; Zhang, Yawen; Habas, Susan E.; Yang, Peidong; Somorjai, Gabor A.

    2008-05-09

    Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as {approx}1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H{sub 2} after reduction (76 torr of H{sub 2} mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.

  20. Catalytic heat exchangers for small-scale production of hydrogen - feasibility study

    Energy Technology Data Exchange (ETDEWEB)

    Silversand, F. [Catator AB, Lund (Sweden)

    2002-02-01

    A feasibility study concerning heat-exchanger reactors in small-scale production of hydrogen has been performed on the request of Svenskt Gastekniskt Center AB and SWEP International AB. The basic idea is to implement different catalysts into brazed plate-type heat exchangers. This can be achieved by installing catalytic cylinders in the inlet-and outlet ports of the heat exchangers or through treatment of the plates to render them catalytically active. It is also possible to sandwich catalytically active wire meshes between the plates. Experiments concerning steam reforming of methanol and methane have been performed in a micro-reactor to gather kinetic data for modelling purposes. Performance calculations concerning heat exchanger reactors have then been conducted with Catator's generic simulation code for catalytic reactors (CatalystExplorer). The simulations clearly demonstrate the technical performance of these reactors. Indeed, the production rate of hydrogen is expected to be about 10 nm{sup 3}/h per litre of heat exchanger. The corresponding value for a conventional steam-reforming unit is about 1 nm{sup 3}/h or less per litre of reactor volume. Also, the compactness and the high degree of integration together with the possibilities of mass production will give an attractive cost for such units. Depending on the demands concerning the purity of the hydrogen it is possible to add secondary catalytic steps like water-gas shifters, methanation and selective oxidation, into a one-train unit, i.e. to design an all-inclusive design. Such reactors can be used for the supply of hydrogen to fuel cells. The production cost for hydrogen can be cut by 60 - 70% through the utilisation of heat exchanger reactors instead of conventional electrolysis. This result is primarily a result of the high price for electricity compared to the feed stock prices in steam reforming. It is important to verify the performance calculations and the simulation results through

  1. Nitrogen-Doped Graphene for Photocatalytic Hydrogen Generation.

    Science.gov (United States)

    Chang, Dong Wook; Baek, Jong-Beom

    2016-04-20

    Photocatalytic hydrogen (H2 ) generation in a water splitting process has recently attracted tremendous interest because it allows the direct conversion of clean and unlimited solar energy into the ideal energy resource of H2 . For efficient photocatalytic H2 generation, the role of the photocatalyst is critical. With increasing demand for more efficient, sustainable, and cost-effective photocatalysts, various types of semiconductor photocatalysts have been intensively developed. In particular, on the basis of its superior catalytic and tunable electronic properties, nitrogen-doped graphene is a potential candidate for a high-performance photocatalyst. Nitrogen-doped graphene also offers additional advantages originating from its unique two-dimensional sp(2) -hybridized carbon network including a large specific surface area and exceptional charge transport properties. It has been reported that nitrogen-doped graphene can play diverse but positive functions including photo-induced charge acceptor/meditator, light absorber from UV to visible light, n-type semiconductor, and giant molecular photocatalyst. Herein, we summarize the recent progress and general aspects of nitrogen-doped graphene as a photocatalyst for photocatalytic H2 generation. In addition, challenges and future perspectives in this field are also discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Substrate-mediated enhanced activity of Ru nanoparticles in catalytic hydrogenation of benzene

    KAUST Repository

    Liu, Xin

    2012-01-01

    The impact of carbon substrate-Ru nanoparticle interactions on benzene and hydrogen adsorption that is directly related to the performance in catalytic hydrogenation of benzene has been investigated by first-principles based calculations. The stability of Ru 13 nanoparticles is enhanced by the defective graphene substrate due to the hybridization between the dsp states of the Ru 13 particle with the sp 2 dangling bonds at the defect sites. The local curvature formed at the interface will also raise the Ru atomic diffusion barrier, and prohibit the particle sintering. The strong interfacial interaction results in the shift of averaged d-band center of the deposited Ru nanoparticle, from -1.41 eV for a freestanding Ru 13 particle, to -1.17 eV for the Ru/Graphene composites, and to -1.54 eV on mesocellular foam carbon. Accordingly, the adsorption energies of benzene are increased from -2.53 eV for the Ru/mesocellular foam carbon composites, to -2.62 eV on freestanding Ru 13 particles, to -2.74 eV on Ru/graphene composites. A similar change in hydrogen adsorption is also observed, and all these can be correlated to the shift of the d-band center of the nanoparticle. Thus, Ru nanoparticles graphene composites are expected to exhibit both high stability and superior catalytic performance in hydrogenation of arenes. © 2012 The Royal Society of Chemistry.

  3. Catalytic process for control of NO.sub.x emissions using hydrogen

    Science.gov (United States)

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2010-05-18

    A selective catalytic reduction process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent. A zirconium sulfate (ZrO.sub.2)SO.sub.4 catalyst support material with about 0.01-2.0 wt. % Pd is applied to a catalytic bed positioned in a flow of exhaust gas at about 70-200.degree. C. The support material may be (ZrO.sub.2--SiO.sub.2)SO.sub.4. H.sub.2O and hydrogen may be injected into the exhaust gas upstream of the catalyst to a concentration of about 15-23 vol. % H.sub.2O and a molar ratio for H.sub.2/NO.sub.x in the range of 10-100. A hydrogen-containing fuel may be synthesized in an Integrated Gasification Combined Cycle power plant for combustion in a gas turbine to produce the exhaust gas flow. A portion of the fuel may be diverted for the hydrogen injection.

  4. Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting.

    Science.gov (United States)

    Rausch, Benjamin; Symes, Mark D; Chisholm, Greig; Cronin, Leroy

    2014-09-12

    The electrolysis of water using renewable energy inputs is being actively pursued as a route to sustainable hydrogen production. Here we introduce a recyclable redox mediator (silicotungstic acid) that enables the coupling of low-pressure production of oxygen via water oxidation to a separate, catalytic hydrogen production step outside the electrolyzer that requires no post-electrolysis energy input. This approach sidesteps the production of high-pressure gases inside the electrolytic cell (a major cause of membrane degradation) and essentially eliminates the hazardous issue of product gas crossover at the low current densities that characterize renewables-driven water-splitting devices. We demonstrated that a platinum-catalyzed system can produce pure hydrogen over 30 times faster than state-of-the-art proton exchange membrane electrolyzers at equivalent platinum loading. Copyright © 2014, American Association for the Advancement of Science.

  5. Contribution to the study of catalytic hydrogen-deuterium exchange between hydrogen and hydrocarbons

    International Nuclear Information System (INIS)

    Ravoire, J.

    1958-01-01

    The hydrogen-deuterium exchange between molecular hydrogen and hydrocarbons over a platinum and charcoal catalyst was studied in a static system. The change in isotopic composition of molecular hydrogen was followed by a thermal conductivity method. Cyclo-pentane and cyclohexane were chosen because of their stability. A reversible inactivation of the catalyst was observed with both hydrocarbons. The reasons for this inactivation are unknown but it was shown that reactivation led to satisfactory reproducibility. A kinetic study was done with cyclohexane in the range 30 to 160 deg. C, and 40 to 360 mm for the pressure of hydrogen, and 10 to 70 mm for the pressure of cyclohexane. The order of the reaction with respect to cyclohexane pressure is always close to zero; the order with respect to that of hydrogen is 0.5 above 100 deg. C. It decreases with increasing temperature and becomes negative (-0.5 at 30 deg. C), characterizing an inhibition by hydrogen. At the same time, the apparent activation energy goes from 6 to 13 kcal/mole. (author) [fr

  6. Role of Hydrogen and Oxygen Activation over Pt and Pd-Doped Composites for Catalytic Hydrogen Combustion.

    Science.gov (United States)

    Singh, Satyapaul A; Vishwanath, Karan; Madras, Giridhar

    2017-06-14

    Removal of excess amount of hydrogen in a catalytic route is a safety measure to be implemented in fuel cell technologies and in nuclear power plants. Hydrogen and oxygen activation are crucial steps for hydrogen combustion that can be achieved by modifying supports with suitable noble metals. In the present study, Pt- and Pd-substituted Co 3 O 4 -ZrO 2 (CZ) were synthesized using PEG-assisted sonochemical synthesis. Ionic states of Pt and Pd in CZ supports were analyzed by X-ray photoelectron spectroscopy. Pd and Pt improved H 2 and O 2 activation extensively, which reduced the temperature of 50% conversion (T 50% ) to 33 °C compared with the support (CZ). The activation energy of PdCZ catalyst was decreased by more than 2 folds (13.4 ± 1.2 kJ mol -1 ) compared with CZ (34.3 ± 2.3 kJ mol -1 ). The effect of oxygen vacancies in the reaction mechanism is found to be insignificant with Pt- and Pd-substituted CZ supports. However, oxygen vacancies play an important role when CZ alone was used as catalyst. The importance of hydrogen and oxygen activation as well as the oxygen vacancies in mechanism was studied by H 2 -TPD, H 2 -TPR, and in situ FTIR spectroscopy.

  7. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    McCrea, Keith Ryan [Univ. of California, Berkeley, CA (United States)

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-σ bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as π-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can give

  8. Photocatalysis in Generation of Hydrogen from Water

    KAUST Repository

    Takanabe, Kazuhiro

    2015-04-18

    Solar energy can be converted by utilizing the thermal or photoelectric effects of photons. Concentrated solar power systems utilize thermal energy from the sun by either making steam and then generating power or shifting the chemical equilibrium of a reaction (e.g., water splitting or CO2 reduction) that occurs at extremely high temperatures. The photocatalytic system contains powder photocatalysts. Each photocatalyst particle should collect sufficient photons from the solar flux to cause the required multielectron reactions to occur. The band gap and band edge positions of semiconductors are the most critical parameters for assessing the suitability of photocatalysts for overall water splitting. The most important requirement when selecting photocatalyst materials is the band positions relative to hydrogen and oxygen evolution potentials. For most photocatalysts, surface modification by cocatalysts was found to be essential to achieve overall water splitting.

  9. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

    Full Text Available Complex hydride systems for hydrogen (H2 generation for supplying fuel cells are being reviewed. In the first group, the hydride systems that are capable of generating H2 through a mechanical dehydrogenation phenomenon at the ambient temperature are discussed. There are few quite diverse systems in this group such as lithium alanate (LiAlH4 with the following additives: nanoiron (n-Fe, lithium amide (LiNH2 (a hydride/hydride system and manganese chloride MnCl2 (a hydride/halide system. Another hydride/hydride system consists of lithium amide (LiNH2 and magnesium hydride (MgH2, and finally, there is a LiBH4-FeCl2 (hydride/halide system. These hydride systems are capable of releasing from ~4 to 7 wt.% H2 at the ambient temperature during a reasonably short duration of ball milling. The second group encompasses systems that generate H2 at slightly elevated temperature (up to 100 °C. In this group lithium alanate (LiAlH4 ball milled with the nano-Fe and nano-TiN/TiC/ZrC additives is a prominent system that can relatively quickly generate up to 7 wt.% H2 at 100 °C. The other hydride is manganese borohydride (Mn(BH42 obtained by mechano-chemical activation synthesis (MCAS. In a ball milled (2LiBH4 + MnCl2 nanocomposite, Mn(BH42 co-existing with LiCl can desorb ~4.5 wt.% H2 at 100 °C within a reasonable duration of dehydrogenation. Practical application aspects of hydride systems for H2 generation/storage are also briefly discussed.

  10. Hydrogen Generation Rate Scoping Study of DOW Corning Antifoam Agent

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, Charles

    2005-09-27

    The antifoam agent DOW Corning Q2-3183A will be added to waste streams in the Hanford River Protection Program-Waste Treatment and Immobilization Plant (RPP-WTP) to prevent foaming. It consists mostly of polydimethylsiloxane (PDMS) and polypropylene glycol (PPG). These and other minor constituents of the antifoam have organic constituents that may participate in radiolytic and chemical reactions that produce hydrogen in Hanford waste. It has been recommended by The WTP R&T Department recommended personnel to treat the organic compounds of the antifoam like the in a similar manner as other organic compounds that are native to the Hanford waste with respect to hydrogen production. This testing has investigated the radiolytic and thermal production of hydrogen from antifoam added to simulant waste solutions to determine if the organic components of the antifoam produce hydrogen in the same manner as the native organic species in Hanford waste. Antifoam additions for this testing were in the range of 4 to 10 wt% to ensure adequate hydrogen detection. Test conditions were selected to bound exposures to the antifoam agent in the WTP. These levels are higher than previously recommended values of 350 mg/L for actual applications in WTP tanks containing air spargers and pulse jet mixers. Limited degradation analyses for the organic components of the antifoam were investigated in this study. A more detailed study involving analyses of antifoam degradation and product formation is in progress at SRNL and results from that study will be reported at a later time. The total organic carbon (TOC) content of the Q2-3183A antifoam was measured to be 39.7 {+-} 4.9 wt% TOC. This measurement was performed in triplicate with on three different dilutions of the pure antifoam liquid using a TOC combustion analyzer instrument with catalytic oxidation, followed by CO{sub 2} quantification using an infrared detector. Test results from this study indicate that the WTP HGR correlation

  11. PA-Tb-Cu MOF as luminescent nanoenzyme for catalytic assay of hydrogen peroxide.

    Science.gov (United States)

    Qi, Zewan; Wang, Li; You, Qi; Chen, Yang

    2017-10-15

    Metal organic frameworks (MOFs) with flexible structures and components have aroused great interest in designing functional materials. In this work, we designed and made a kind of PA-Tb-Cu MOF nanoenzyme capable of emitting fluorescence for the catalytic reaction of hydrogen peroxide (H 2 O 2 ). Luminescent Tb 3+ , catalytic Cu 2+ and bridging ligand were assembled and integrated into a single material nanoenzyme. This PA-Tb-Cu MOF nanoenzyme not only possessed excellent catalytic activity comparable to horseradish peroxidase but also can real-time fluorescently indicate the concentration of H 2 O 2 as low as 0.2µM during catalysis. Luminescent PA-Tb-Cu MOF nanoenzyme did not need a common combined use of natural/artificial enzymes and chromogenic reactions for the quantification of H 2 O 2 in widely-used enzyme-catalytic reactions. The present strategy assembled directly from functional ions/molecules provides a new way for the design and development of smart, multifunctional artificial enzymes for wide applications in biocatalysis, bioassays and nano-biomedicine. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Continuous catalytic hydrogenation of polyaromatic hydrocarbon compounds in hydrogen-supercritical carbon dioxide.

    Science.gov (United States)

    Yuan, Tao; Fournier, Anick R; Proudlock, Raymond; Marshall, William D

    2007-03-15

    A continuous hydrogenation device was evaluated for the detoxification of selected tri-, tetra-, or pentacyclic polyaromatic hydrocarbon (PAH) compounds {anthracene, phenanthrene, chrysene, and benzo[a]pyrene (B[a]P)} by hydrogenation. A substrate stream in hexane, 0.05-1.0% (w/v), was mixed with hydrogen-carbon dioxide (H2-CO2, 5-30% v/v) and delivered to a heated reactor column (25 cm x 1 cm) containing palladium supported on gamma alumina (Pd0/gamma-Al2O3) that was terminated with a capillary restrictor. The flow rate from the reactor, approximately 800 mL min(-1) decompressed gas, corresponded to 4 mL min(-1) fluid under the operating conditions of the trials. Reaction products were recovered by passing the reactor effluent through hexane. At 90 degrees C, the anthracene or phenanthrene substrate was hydrogenated only partially to octahydro and dodecahydro species and contained only a minor quantity of totally hydrogenated products. For substrates with increasing numbers of fused aromatic rings, the hydrogenation efficiency was decreased further. However, at an increasing temperature (90-150 degrees C) and increasing mobile phase flow rate (20.68 MPa corresponding to 2100 mL min(-1) decompressed gas), B[a]P and chrysene were hydrogenated, virtuallytotally, to their corresponding perhydro analogues (eicosahydrobenzo[a]pyrenes and octadecahydrochrysenes), respectively. That this approach might be useful for decontaminating soil extracts was supported by companion in vitro trials in which the substrate and products were assayed for mutagenic activity with five bacterial strains that are auxotrophic for histidine (Salmonella typhimurium TA98, TA100, TA1535, and TA1537) or tryptophan (Escherichia coliWP2 uvrA), using the bacterial reverse mutation assay (modified Ames test). Generally, substantial increases in revertant colony counts were not observed with any of the strains following exposure to the hydrogenation products in the absence or presence of the 10 or 30

  13. Detailed modelling of processes inside a catalytic recombiner for hydrogen removal

    International Nuclear Information System (INIS)

    Heitsch, M.

    1999-01-01

    Under accidental conditions, considerable amounts of hydrogen may be released into the containment. Catalytic reacting surfaces in recombiners are a reliable method to recombine this hydrogen and other burnable gases like carbon monoxide from the atmosphere in a passive way. Many experiments have been carried out to study the main phenomena occurring inside recombiners, like the efficiency of hydrogen removal, the start-up conditions, poisoning, oxygen starvation, steam and water impact, and others. In addition, the global behavior of a given recombiner device in a larger environment has been investigated in order to demonstrate the effectiveness and to facilitate the derivation of simplified models for long term, severe accident analyses. These long-term severe accident models are complemented by detailed investigations to understand the interaction of chemistry and flow inside a recombiner box. This helps to provide the dependencies of non-measurable variables (e.g. the reaction rate distribution), of local surface temperatures etc. to make long-term or system models more reliable. It also offers possibilities for increasing the chemical efficiency by optimising the geometric design properly. Computational Fluid Dynamics (CFD) codes are available for use as development tools to include the specifics of catalytic surface reactors. The present paper describes the use of the code system CFX [1] for creating a recombiner model. Some model predictions are compared to existing test data. (author)

  14. Induced Superaerophobicity onto a Non-superaerophobic Catalytic Surface for Enhanced Hydrogen Evolution Reaction.

    Science.gov (United States)

    Akbar, Kamran; Hussain, Sajjad; Truong, Linh; Roy, Sanjib Baran; Jeon, Jae Ho; Jerng, Sahng-Kyoon; Kim, Minsoo; Yi, Yeonjin; Jung, Jongwan; Chun, Seung-Hyun

    2017-12-20

    Despite tremendous progress in the development of novel electrocatalysts for hydrogen evolution reaction (HER), the accumulation of hydrogen gas bubbles produced on the catalyst surface has been rather poorly addressed. The bubbles block the surface of the electrode, thus resulting in poor performance even when excellent electrocatalysts are used. In this study, we show that vertically grown graphene nanohills (VGNHs) possess an excellent capability to quickly disengage the produced hydrogen gas bubbles from the electrode surface, and thus exhibit superaerophobic properties. To compensate for the poor electrolytic properties of graphene toward HER, the graphene surface was modified with WS 2 nanoparticles to accelerate the water-splitting process by using this hybrid catalyst (VGNHs-WS 2 ). For comparison purposes, WS 2 nanoparticles were also deposited on the flat graphene (FG) surface. Because of its superior superaerophobic properties, VGNHs-WS 2 outperformed FG-WS 2 in terms of both catalytic activity toward the HER and superaerophobicity. Furthermore, VGNHs-WS 2 exhibited a low onset potential (36 mV compared to 288 mV for FG-WS 2 ) and long-term stability in the HER over an extended period of 20 h. This study provides an efficient way to utilize highly conductive and superaerophobic VGNHs as support materials for intrinsic semiconductors, such as WS 2 , to simultaneously achieve superaerophobicity and high catalytic activity.

  15. New nanosized catalytic membrane reactors for hydrogenation with stored hydrogen: Prerequisites and the experimental basis for their creation

    Science.gov (United States)

    Soldatov, A. P.; Tsodikov, M. V.; Parenago, O. P.; Teplyakov, V. V.

    2010-12-01

    The prerequisites and prospects for creating a new generation of nanosized membrane reactors are considered. For the first time, hydrogenation reactions take place in ceramic membrane pores with hydrogen adsorbed beforehand in mono- and multilayered oriented carbon nanotubes with graphene walls (OCNTGs) formed on the internal pore surface. It is shown for Trumem microfiltration membranes with D avg ˜130 nm that oxidation reactions of CO on a Cu0.03Ti0.97O2 ± δ catalyst and the oxidative conversion of methane into synthesis gas and light hydrocarbons on La + Ce/MgO are considerably enhanced when they occur in membranes. Regularities of hydrogen adsorption, storage, and desorption in nanosized membrane reactors are investigated through OCNTG formation in Trumem ultrafiltration membrane pores with D avg = 50 and 90 nm and their saturation with hydrogen at a pressure of 10-13 MPa. It is shown that the amount of adsorbed hydrogen reaches 14.0% of OCNTG mass. Using thermogravimetric analysis in combination with mass-spectrometric analysis, hydrogen adsorption in OCNTG is first determined and its desorption is found to proceed at atmospheric pressure at a temperature of ˜175°C. It is shown that adsorbed hydrogen affects the transport properties of the membranes, reducing their efficiency with respect to liquids by 4-26 times. This is indirect confirmation of its high activity, due apparently the dissociative mechanism of adsorption.

  16. Catalytic hydrogenation of CO2 over Pt- and Ni-doped graphene: A comparative DFT study.

    Science.gov (United States)

    Esrafili, Mehdi D; Sharifi, Fahimeh; Dinparast, Leila

    2017-10-01

    Today, the global greenhouse effect of carbon dioxide (CO 2 ) is a serious environmental problem. Therefore, developing efficient methods for CO 2 capturing and conversion to valuable chemicals is a great challenge. The aim of the present study is to investigate the catalytic activity of Pt- or Ni-doped graphene for the hydrogenation of CO 2 by a hydrogen molecule. To gain a deeper insight into the catalytic mechanism of this reaction, the reliable density functional theory calculations are performed. The adsorption energies, geometric parameters, reaction barriers, and thermodynamic properties are calculated using the M06-2X density functional. Two reaction mechanisms are proposed for the hydrogenation of CO 2 . In the bimolecular mechanism, the reaction proceeds in two steps, initiating by the co-adsorption of CO 2 and H 2 molecules over the surface, followed by the formation of a OCOH intermediate by the transfer of H atom of H 2 toward O atom of CO 2 . In the next step, formic acid is produced as a favorable product with the formation of CH bond. In our proposed termolecular mechanism, however, H 2 molecule is directly activated by the two pre-adsorbed CO 2 molecules. The predicted activation energy for the formation of the OCOH intermediate in the bimolecular mechanism is 20.8 and 47.9kcalmol -1 over Pt- and Ni-doped graphene, respectively. On the contrary, the formation of the first formic acid in the termolecular mechanism is found as the rate-determining step over these surfaces, with an activation energy of 28.8 and 45.5kcal/mol. Our findings demonstrate that compared to the Ni-doped graphene, the Pt-doped surface has a relatively higher catalytic activity towards the CO 2 reduction. These theoretical results could be useful in practical applications for removal and transformation of CO 2 to value-added chemical products. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Activating basal-plane catalytic activity of two-dimensional MoS2 monolayer with remote hydrogen plasma

    KAUST Repository

    Cheng, Chia-Chin

    2016-09-10

    Two-dimensional layered transition metal dichalcogenide (TMD) materials such as Molybdenum disufide (MoS2) have been recognized as one of the low-cost and efficient electrocatalysts for hydrogen evolution reaction (HER). The crystal edges that account for a small percentage of the surface area, rather than the basal planes, of MoS2 monolayer have been confirmed as their active catalytic sites. As a result, extensive efforts have been developing in activating the basal planes of MoS2 for enhancing their HER activity. Here, we report a simple and efficient approach-using a remote hydrogen-plasma process-to creating S-vacancies on the basal plane of monolayer crystalline MoS2; this process can generate high density of S-vacancies while mainly maintaining the morphology and structure of MoS2 monolayer. The density of S-vacancies (defects) on MoS2 monolayers resulted from the remote hydrogen-plasma process can be tuned and play a critical role in HER, as evidenced in the results of our spectroscopic and electrical measurements. The H2-plasma treated MoS2 also provides an excellent platform for systematic and fundamental study of defect-property relationships in TMDs, which provides insights for future applications including electrical, optical and magnetic devices. © 2016 Elsevier Ltd.

  18. On-board hydrogen generation for PEM fuel cell vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Vanderborgh, N. E.; Tafoya, J.; Inbody, M. [Los Alamos National Laboratory, Fuel Cell Engineering, Los Alamos, NM (United States)

    1999-10-01

    Hydrogen powered fuel cell vehicles are considered by many as the transportation technology for the 21. century, primarily because of hydrogen`s high efficiency and zero, or near-zero emission of pollutants to the atmosphere. First generation hydrogen technology demonstrated the feasibility of using compressed hydrogen as automotive fuel, but these vehicles can also be operated with fuel utilized for on-board hydrogen generation. Available evidence suggest that perfecting this new technology would result in simplified refueling and extended vehicle range. This paper reviews the present state of the technology of generating hydrogen on-board, and concludes that at present, there is no clear `winner` between vehicles using stored hydrogen as fuel or vehicles which incorporate on-board hydrogen generation from stored fuel. Both approaches have specific merit, and both may be broadly employed. Indeed, valid economic arguments can be made that centralized hydrogen generation could be more attractive than on-board generation, however, in the view of this author, these arguments are not convincing. His view of the various suggestions about potential fuel sources for transportation in the 21. century (petroleum, liquid natural gas) is that each of these fuels involve having to deal with carbon, which means that new pathways must be invented for managing carbon dioxide. The challenge then is to develop technologies which will result in methane energy production without concurrent carbon dioxide emissions. 13 refs., 2 figs.

  19. An investigation of turbulent catalytically stabilized channel flow combustion of lean hydrogen - air mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Mantzaras, I.; Benz, P.; Schaeren, R.; Bombach, R. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The catalytically stabilised thermal combustion (CST) of lean hydrogen-air mixtures was investigated numerically in a turbulent channel flow configuration using a two-dimensional elliptic model with detailed heterogeneous and homogeneous chemical reactions. Comparison between turbulent and laminar cases having the same incoming mean properties shows that turbulence inhibits homogeneous ignition due to increased heat transport away from the near-wall layer. The peak root-mean-square temperature and species fluctuations are always located outside the extent of the homogeneous reaction zone indicating that thermochemical fluctuations have no significant influence on gaseous combustion. (author) 4 figs., 6 refs.

  20. Theoretical study of catalytic hydrogenation of oxirane and its methyl derivative

    Directory of Open Access Journals (Sweden)

    U.A. Kuevi

    2012-12-01

    Full Text Available Oxirane (C2H4O is an unsaturated heterocyclic compound and methyloxirane (C3H6O is its methyl derivative. Theoretical studies on catalytic hydrogenation of both compounds, in presence of aluminium chloride (AlCl3 catalyst, are carried out. The products of reactions are ethanol and propan-1-ol from oxirane and methyloxirane, respectively. According to the variations of chemical parameters throughout the processes, the mechanisms of both reactions have been proposed.DOI: http://dx.doi.org/10.4314/bcse.v26i3.13

  1. Application of solid state catalytic hydrogen isotope exchange to the tritium labeling of lyoszyme

    International Nuclear Information System (INIS)

    Filikov, A.V.; Jones, J.R.

    1995-01-01

    Solid state catalytic hydrogen isotope exchange has been employed to label hen egg lysozyme with tritium. Optimization of reaction conditions so that amino acids and peptide bonds remained intact led to a tritiated products with 97% of the original enzymatic activity and 94% radiochemical purity. The specific activity when using a T 2 :H 2 mixture of 1:1000, was 16 mCi·mmol -1 . It is suggested that the currently adopted approach may have wide applications for other proteins able to tolerate lyophilization conditions without loss of activity. (Author)

  2. Molecular Self-Assembly Strategy for Generating Catalytic Hybrid Polypeptides.

    Science.gov (United States)

    Maeda, Yoshiaki; Fang, Justin; Ikezoe, Yasuhiro; Pike, Douglas H; Nanda, Vikas; Matsui, Hiroshi

    2016-01-01

    Recently, catalytic peptides were introduced that mimicked protease activities and showed promising selectivity of products even in organic solvents where protease cannot perform well. However, their catalytic efficiency was extremely low compared to natural enzyme counterparts presumably due to the lack of stable tertiary fold. We hypothesized that assembling these peptides along with simple hydrophobic pockets, mimicking enzyme active sites, could enhance the catalytic activity. Here we fused the sequence of catalytic peptide CP4, capable of protease and esterase-like activities, into a short amyloidogenic peptide fragment of Aβ. When the fused CP4-Aβ construct assembled into antiparallel β-sheets and amyloid fibrils, a 4.0-fold increase in the hydrolysis rate of p-nitrophenyl acetate (p-NPA) compared to neat CP4 peptide was observed. The enhanced catalytic activity of CP4-Aβ assembly could be explained both by pre-organization of a catalytically competent Ser-His-acid triad and hydrophobic stabilization of a bound substrate between the triad and p-NPA, indicating that a design strategy for self-assembled peptides is important to accomplish the desired functionality.

  3. Fuel cell drive system with hydrogen generation in test

    Science.gov (United States)

    Emonts, B.; Bøgild Hansen, J.; Schmidt, H.; Grube, T.; Höhlein, B.; Peters, R.; Tschauder, A.

    In the future, drive systems for vehicles with polymer electrolyte membrane fuel cells (PEMFC) may be the environmentally more acceptable alternative to conventional drives with internal combustion engines. The energy carrier may not be gasoline or diesel, as in combustion engines today, but methanol, which is converted on-board into a hydrogen-rich synthesis gas in a reforming reaction with water. After removal of carbon monoxide in a gas-cleaning step, the conditioned synthesis gas is converted into electricity in a fuel cell using air as the oxidant. The electric energy thus generated serves to supply a vehicle's electric drive system. Based on the process design for a test drive system, a test facility was prepared and assembled at Forschungszentrum Jülich (FZJ). Final function tests with the PEMFC and the integrated compact methanol reformer (CMR) were carried out to determine the performance and the dynamic behaviour. With regard to the 50-kW(H 2)-compact methanol reformer, a special design of catalytic burner was constructed. The burner units, with a total power output of 16 kW, were built and tested under different states of constant and alternating load. If selecting a specific catalyst loading of 40 g Pt/m 2, the burner emissions are below the super ultra low emission vehicle (SULEV) standard. The stationary performance test of the CMR shows a specific hydrogen production of 6.7 m N3/(kg cat h) for a methanol conversion rate of 95% at 280°C. Measurements of the transient behaviour of the CMR clearly show a response time of about 20 s, reaching 99% of the hydrogen flow demand due to the limited performance of the test facility control system. Simulations have been carried out in order to develop a control strategy for hydrogen production by the CMR during the New European Driving Cycle (NEDC). Based on the NEDC, an optimized energy management for the total drive system was evaluated and the characteristic data for different peak load storage systems are

  4. Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

    Science.gov (United States)

    Li, Xing-long; Ning, Shen; Yuan, Li-xia; Li, Quan-xin

    2011-08-01

    We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H2 yield (about 20%-50%). The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H2O. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

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

    Directory of Open Access Journals (Sweden)

    Salmi T.

    2000-01-01

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

  6. Effects of current upon hydrogen production from electrochemical catalytic reforming of acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yaqiong; Yuan, Lixia; Ye, Tongqi; Qiu, Songbai; Zhu, Xifeng; Li, Quanxin [Department of Chemical Physics, Lab of Biomass Clean Energy, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); Torimoto, Youshifumi [Oxy Japan Corporation, 7 Floor, Miya Building, 4-3-4, Kojimachi, Chiyoda-ku, Tokyo 102-0083 (Japan); Yamamoto, Mitsuo [College of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902 (Japan)

    2009-02-15

    Production of hydrogen from acetic acid (HAc) was performed by using a novel electrochemical catalytic reforming (ECR) approach over the 18%NiO/Al{sub 2}O{sub 3} catalyst. ECR was carried out in a fixed-bed continuous flow reactor, where an ac electric current was passed through the catalyst. A high yield of hydrogen (>90%) and carbon conversion (>90%) were obtained as the reforming temperature over 400 C via the ECR approach. The influences of the current on the HAc decomposition, its reforming, and the catalyst reduction in the ECR process have been investigated, which were compared with those in the common steam reforming (CSR) route. The mechanism of the HAc reforming in ECR was also discussed based on the present investigation. (author)

  7. Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation

    OpenAIRE

    Sumerin, Victor

    2011-01-01

    Organocatalysis, the use of organic molecules as catalysts, is attracting increasing attention as one of the most modern and rapidly growing areas of organic chemistry, with countless research groups in both academia and the pharmaceutical industry around the world working on this subject. The literature review of this thesis mainly focuses on metal-free systems for hydrogen activation and organocatalytic reduction. Since these research topics are relatively new, the literature review al...

  8. Hydrogen generation behaviors of NaBH4-NH3BH3 composite by hydrolysis

    Science.gov (United States)

    Xu, Yanmin; Wu, Chaoling; Chen, Yungui; Huang, Zhifen; Luo, Linshan; Wu, Haiwen; Liu, Peipei

    2014-09-01

    In this work, NH3BH3 (AB) is used to induce hydrogen generation during NaBH4 (SB) hydrolysis in order to reduce the use of catalysts, simplify the preparation process, reduce the cost and improve desorption kinetics and hydrogen capacity as well. xNaBH4-yNH3BH3 composites are prepared by ball-milling in different proportions (from x:y = 1:1 to 8:1). The experimental results demonstrate that all composites can release more than 90% of hydrogen at 70 °C within 1 h, and their hydrogen yields can reach 9 wt% (taking reacted water into account). Among them, the composites in the proportion of 4:1 and 5:1, whose hydrogen yields reach no less than 10 wt%, show the best hydrogen generation properties. This is due to the impact of the following aspects: AB additive improves the dispersibility of SB particles, makes the composite more porous, hampers the generated metaborate from adhering to the surface of SB, and decreases the pH value of the composite during hydrolysis. The main solid byproduct of this hydrolysis system is NaBO2·2H2O. By hydrolytic kinetic simulation of the composites, the fitted activation energies of the complexes are between 37.2 and 45.6 kJ mol-1, which are comparable to the catalytic system with some precious metals and alloys.

  9. A self-catalytic mixed-conducting membrane reactor for effective production of hydrogen from methane

    Science.gov (United States)

    Dong, Xueliang; Liu, Zhengkun; Jin, Wanqin; Xu, Nanping

    A supported mixed-conducting LNCO membrane with a pore-gradient structure LNO support was successfully prepared via a dry pressing and co-sintering route. The match of sintering behaviors between membrane and support was realized by the preparation of an ABB‧B‧‧B‧BA-type membrane. A scanning electron microscopy (SEM) test demonstrated that the surface of the supported membrane was dense and crack-free and the pore-gradient structure of the support can be observed clearly. The oxygen flux of the supported membrane was about 5.6 times that of the symmetric LNCO membrane. A self-catalytic mixed-conducting membrane reactor was constructed using the prepared membrane for hydrogen production from methane. It was found that this membrane reactor exhibited high performance and good stability for hydrogen production. At 1123 K, the CH 4 conversion, hydrogen selectivity and hydrogen production remained at about 60%, 89% and 8.0 ml(STP) cm -2 min -1, respectively, for more than 120 h.

  10. Catalytic Transfer Hydrogenation of Biomass-Derived Carbonyls over Hafnium-Based Metal-Organic Frameworks.

    Science.gov (United States)

    Rojas-Buzo, Sergio; García-García, Pilar; Corma, Avelino

    2018-01-23

    A series of highly crystalline, porous, hafnium-based metal-organic frameworks (Hf-MOFs) have been shown to catalyze the transfer hydrogenation reaction of levulinic ester to produce γ-valerolactone by using isopropanol as a hydrogen donor. The results are compared with their zirconium-based counterparts. The role of the metal center in Hf-MOFs has been identified and reaction parameters optimized. NMR studies using isotopically labeled isopropanol provide evidence that the transfer hydrogenation occurs through a direct intermolecular hydrogen transfer route. The catalyst, Hf-MOF-808, can be recycled several times with only a minor decrease in catalytic activity. The generality of the procedure has been demonstrated by accomplishing the transformation with aldehydes, ketones, and α,β-unsaturated carbonyl compounds. The combination of Hf-MOF-808 with the Brønsted-acidic Al-Beta zeolite gives the four-step one-pot transformation of furfural to γ-valerolactone in good yield of 75 %. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Room temperature hydrogen generation from hydrolysis of ammonia-borane over an efficient NiAgPd/C catalyst

    KAUST Repository

    Hu, Lei

    2014-12-01

    NiAgPd nanoparticles are successfully synthesized by in-situ reduction of Ni, Ag and Pd salts on the surface of carbon. Their catalytic activity was examined in ammonia borane (NH3BH3) hydrolysis to generate hydrogen gas. This nanomaterial exhibits a higher catalytic activity than those of monometallic and bimetallic counterparts and a stoichiometric amount of hydrogen was produced at a high generation rate. Hydrogen production rates were investigated in different concentrations of NH3BH3 solutions, including in the borates saturated solution, showing little influence of the concentrations on the reaction rates. The hydrogen production rate can reach 3.6-3.8 mol H2 molcat -1 min-1 at room temperature (21 °C). The activation energy and TOF value are 38.36 kJ/mol and 93.8 mol H2 molcat -1 min-1, respectively, comparable to those of Pt based catalysts. This nanomaterial catalyst also exhibits excellent chemical stability, and no significant morphology change was observed from TEM after the reaction. Using this catalyst for continuously hydrogen generation, the hydrogen production rate can be kept after generating 6.2 L hydrogen with over 10,000 turnovers and a TOF value of 90.3 mol H2 molcat -1 min-1.

  12. Effects of acido-basic support properties on the catalytic hydrogenation of acetylene on gold nano-particles

    Science.gov (United States)

    Manda, Abdullah Ahmed

    Metallic gold nanoparticles supported on gamma-Al2O 3 and magnesia-alumina mixed oxide, with different magnesia content have been prepared by sol-gel method and characterized by different techniques (inductive coupled plasma-mass spectroscopy (ICP-MS), XRD, BET surface area analysis, transmission electron microscopy (TEM), CO2 and NH 3 temperature programmed desorption (TPD), H2 temperature programmed reduction (TPR) and FTIR of adsorbed CO2). Such systems were found to produce catalysts with controllable acidity, varying from catalyst possessing large density of acidic and low density of basic sites, others with acidic and basic sites of equal strength and density, and others with large basic and low acid sites densities, respectively. The catalytic assessment of the generated acidity was carried out using 2-propanol decomposition as a test reaction. The results obtained indicate that the presence of magnesia and reduced gold nanopartilces has imparted the catalysts, 1%Au/4%Mg-Al 2O3 and 1%Au/8%Mg-Al2O3, with significant base-catalytic properties. Acetylene hydrogenation and formation of coke deposits were investigated on a gold catalyst supported on gamma-Al2O3 and gold supported on alumina-magnisia mixed oxide with different gold content; 1%Au/gamma-Al 2O3, 1%Au/15%Mg-Al2O3, 2%Au/15%Mg-Al 2O3 and 4%Au/15%Mg-Al2O3. The effect of the H2/C2H2 ratio was studied over a range of values. The catalytic activity and selectivity towards ethylene and other products were investigated at different reaction temperatures. Acetylene hydrogenation was investigated in the presence and absence of ethylene in stream. It is investigated that the adsorption of the triple bond is preferred over the double bond and during selective catalytic (SCR) of C2H2 the two hydrocarbons do not compete for the same adsorption sites. The deactivation of catalysts was studied by temperature programmed oxidation (TPO). Higher content of coke over 1%Au/Al2O3 catalyst was investigated in contrast to

  13. Biomass to hydrogen-rich syngas via catalytic steam gasification of bio-oil/biochar slurry.

    Science.gov (United States)

    Chen, Guanyi; Yao, Jingang; Liu, Jing; Yan, Beibei; Shan, Rui

    2015-12-01

    The catalytic steam gasification of bio-oil/biochar slurry (bioslurry) for hydrogen-rich syngas production was investigated in a fixed-bed reactor using LaXFeO3 (X=Ce, Mg, K) perovskite-type catalysts. The effects of elemental substitution in LaFeO3, temperature, water to carbon molar ratio (WCMR) and bioslurry weight hourly space velocity (WbHSV) were examined. The results showed that La0.8Ce0.2FeO3 gave the best performance among the prepared catalysts and had better catalytic activity and stability than the commercial 14 wt.% Ni/Al2O3. The deactivation caused by carbon deposition and sintering was significantly depressed in the case of La0.8Ce0.2FeO3 catalyst. Both higher temperature and lower WbHSV contributed to more H2 yield. The optimal WCMR was found to be 2, and excessive introducing of steam reduced hydrogen yield. The La0.8Ce0.2FeO3 catalyst gave a maximum H2 yield of 82.01% with carbon conversion of 65.57% under the optimum operating conditions (temperature=800°C, WCMR=2 and WbHSV=15.36h(-1)). Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Nano-hetero functional materials for photocatalytic hydrogen generation

    Science.gov (United States)

    Tongying, Pornthip

    This dissertation focuses on designing nanomaterials and investigating their photocatalytic response for H2 generation. Hydrogen has gained a lot of attention as a new source of sustainable energy. It can be used to directly generate power in fuel cells and to produce liquid fuels such as methanol. Water splitting is an ideal (clean) way of producing H2 because it uses water and sunlight, two renewable resources. To explore the use of nanostructures and particularly nanostructure heterojunctions for photocatalytic H2 generation, four different systems have been synthesized: (i) CdSe nanowires (NWs), (ii) CdSe/CdS core/shell NWs, (iii) CdSe NWs decorated with Au or Pt nanoparticles, and (iv) CdSe/CdS NWs decorated with Au or Pt nanoparticles. This is motivated by (a) the fact that CdSe NWs absorb light from the UV to the near infrared (b) the NW morphology simultaneously enables us to explore the role of nanoscale dimensionality in photocatalytic processes (c) a CdS coating can enhance photogenerated carrier lifetimes, and (d) metal nanoparticles are catalytically active and can also enhance charge separation efficiencies. Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. Femtosecond transient differential absorption (TDA) spectroscopy has been used as a tool to reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. The use of this technique in concert with hydrogen evolution tests also reveal how CdS, CdSe and metal NP interact within metal NP decorated CdSe and CdSe/CdS NWs during photocatalytic hydrogen generation reactions. Electron transfer events across both semiconductor/semiconductor and metal/semiconductor heterojunctions are followed to identify where H 2 is evolved and the role each heterojunction plays in determining a system's overall

  15. Surface generation of negative hydrogen ion beams

    International Nuclear Information System (INIS)

    Bommel, P.J.M. van.

    1984-01-01

    This thesis describes investigations on negative hydrogen ion sources at the ampere level. Formation of H - ions occurs when positive hydrogen ions capture two electrons at metal surfaces. The negative ionization probability of hydrogen at metal surfaces increases strongly with decreasing work function of the surface. The converters used in this study are covered with cesium. Usually there are 'surface plasma sources' in which the hydrogen source plasma interacts with a converter. In this thesis the author concentrates upon investigating a new concept that has converters outside the plasma. In this approach a positive hydrogen ion beam is extracted from the plasma and is subsequently reflected from a low work function converter surface. (Auth.)

  16. Pd(II-dissolved in ionic liquids: a recyclable catalytic system for the selective biphasic hydrogenation of dienes to monoenes

    Directory of Open Access Journals (Sweden)

    Dupont Jairton

    2000-01-01

    Full Text Available Palladium acetylacetonate dissolved in 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid catalyses the selective two-phase hydrogenation of conjugated and non-conjugated (functionalized and non-functionalized dienes into the respective monoenes. The system does not require the use of organic solvents, the products are removed by simple decantation or distillation and the recovered ionic catalytic solution can be reused several times without any significant changes in its catalytic activity and selectivity.

  17. Purge gas recovery of ammonia synthesis plant by integrated configuration of catalytic hydrogen-permselective membrane reactor and solid oxide fuel cell as a novel technology

    Science.gov (United States)

    Siavashi, Fakhteh; Saidi, Majid; Rahimpour, Mohammad Reza

    2014-12-01

    The purge gas emission of ammonia synthesis plant which contains hazardous components is one of the major sources of environmental pollution. Using integrated configuration of catalytic hydrogen-permselective membrane reactor and solid oxide fuel cell (SOFC) system is a new approach which has a great impact to reduce the pollutant emission. By application of this method, not only emission of ammonia and methane in the atmosphere is prevented, hydrogen is produced through the methane steam reforming and ammonia decomposition reactions that take place simultaneously in a catalytic membrane reactor. The pure generated hydrogen by recovery of the purge gas in the Pd-Ag membrane reactor is used as a feed of SOFC. Since water is the only byproduct of the electrochemical reaction in the SOFC, it is recycled to the reactor for providing the required water of the reforming reaction. Performance investigation of the reactor represents that the rate of hydrogen permeation increases with enhancing the reactor temperature and pressure. Also modeling results indicate that the SOFC performance improves with increasing the temperature and fuel utilization ratio. The generated power by recovery of the purging gas stream of ammonia synthesis plant in the Razi petrochemical complex is about 8 MW.

  18. Life cycle assessment of hydrogenated biodiesel production from waste cooking oil using the catalytic cracking and hydrogenation method.

    Science.gov (United States)

    Yano, Junya; Aoki, Tatsuki; Nakamura, Kazuo; Yamada, Kazuo; Sakai, Shin-ichi

    2015-04-01

    There is a worldwide trend towards stricter control of diesel exhaust emissions, however presently, there are technical impediments to the use of FAME (fatty acid methyl esters)-type biodiesel fuel (BDF). Although hydrogenated biodiesel (HBD) is anticipated as a new diesel fuel, the environmental performance of HBD and its utilization system have not been adequately clarified. Especially when waste cooking oil is used as feedstock, not only biofuel production but also the treatment of waste cooking oil is an important function for society. A life cycle assessment (LCA), including uncertainty analysis, was conducted to determine the environmental benefits (global warming, fossil fuel consumption, urban air pollution, and acidification) of HBD produced from waste cooking oil via catalytic cracking and hydrogenation, compared with fossil-derived diesel fuel or FAME-type BDF. Combined functional unit including "treatment of waste cooking oil" and "running diesel vehicle for household waste collection" was established in the context of Kyoto city, Japan. The calculation utilized characterization, damage, and integration factors identified by LIME2, which was based on an endpoint modeling method. The results show that if diesel vehicles that comply with the new Japanese long-term emissions gas standard are commonly used in the future, the benefit of FAME-type BDF will be relatively limited. Furthermore, the scenario that introduced HBD was most effective in reducing total environmental impact, meaning that a shift from FAME-type BDF to HBD would be more beneficial. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei

    2017-11-16

    The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi

    2014-03-01

    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  1. Hydrogen Generation from Sugars via Aqueous-Phase Reforming

    International Nuclear Information System (INIS)

    Randy D Cortright

    2006-01-01

    Virent Energy Systems, Inc. is commercializing the Aqueous Phase Reforming (APR) process that allows the generation of hydrogen-rich gas streams from biomass-derived compounds such as glycerol, sugars, and sugar alcohols. The APR process is a unique method that generates hydrogen from aqueous solutions of these oxygenated compounds in a single step reactor process compared to the three or more reaction steps required for hydrogen generation via conventional processes that utilize non-renewable fossil fuels. The key breakthrough of the APR process is that the reforming of these aqueous solutions is done in the liquid phase. The patented APR process occurs at temperatures (150 C to 270 C) where the water-gas shift reaction is favorable, making it possible to generate hydrogen with low amounts of CO in a single chemical reactor. Furthermore, the APR process occurs at pressures (typically 15 to 50 bar) where the hydrogen-rich effluent can be effectively purified using either membrane technology or pressure swing adsorption technology. The utilization of biomass-based compounds allows the APR process to be a carbon neutral method to generate hydrogen. In the near term, the feed-stock of interest is waste glycerol that is being generated in large quantities as a byproduct in the production of bio-diesel. Virent has developed the APR system for on-demand generation of hydrogen-rich fuel gas from either glycerol or sorbitol (the sugar alcohol formed by hydrogenation of glucose) to fuel a stationary internal combustion engine driven generator (10 kW). Under a USDOE funded project, Virent is currently developing the APR process to generate high yields of hydrogen from corn-derived glucose. This project objective is to achieve the DOE 2010 cost target for distributed production from renewable liquid fuels of 3.60 dollars/gge (gasoline gallon equivalent) delivered. (authors)

  2. Catalytic hydrogenation rate of polycyclic aromatic hydrocarbons in supercritical carbon dioxide containing polymer-stabilized palladium nanoparticles.

    Science.gov (United States)

    Liao, Weisheng; Liu, Hsin-Wang; Chen, Hsing-Jung; Chang, Wen-Yen; Chiu, Kong-Hwa; Wai, Chien M

    2011-01-01

    Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO₂ containing 1 MPa of H₂ at 40-50°C. Kinetic studies based on in situ UV/Vis spectra of the CO₂ phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces. Copyright © 2010 Elsevier Ltd. All rights reserved.

  3. Effect of catalytic cylinders on autothermal reforming of methane for hydrogen production in a microchamber reactor.

    Science.gov (United States)

    Yan, Yunfei; Guo, Hongliang; Zhang, Li; Zhu, Junchen; Yang, Zhongqing; Tang, Qiang; Ji, Xin

    2014-01-01

    A new multicylinder microchamber reactor is designed on autothermal reforming of methane for hydrogen production, and its performance and thermal behavior, that is, based on the reaction mechanism, is numerically investigated by varying the cylinder radius, cylinder spacing, and cylinder layout. The results show that larger cylinder radius can promote reforming reaction; the mass fraction of methane decreased from 26% to 21% with cylinder radius from 0.25 mm to 0.75 mm; compact cylinder spacing corresponds to more catalytic surface and the time to steady state is decreased from 40 s to 20 s; alteration of staggered and aligned cylinder layout at constant inlet flow rates does not result in significant difference in reactor performance and it can be neglected. The results provide an indication and optimize performance of reactor; it achieves higher conversion compared with other reforming reactors.

  4. Effect of Catalytic Cylinders on Autothermal Reforming of Methane for Hydrogen Production in a Microchamber Reactor

    Directory of Open Access Journals (Sweden)

    Yunfei Yan

    2014-01-01

    Full Text Available A new multicylinder microchamber reactor is designed on autothermal reforming of methane for hydrogen production, and its performance and thermal behavior, that is, based on the reaction mechanism, is numerically investigated by varying the cylinder radius, cylinder spacing, and cylinder layout. The results show that larger cylinder radius can promote reforming reaction; the mass fraction of methane decreased from 26% to 21% with cylinder radius from 0.25 mm to 0.75 mm; compact cylinder spacing corresponds to more catalytic surface and the time to steady state is decreased from 40 s to 20 s; alteration of staggered and aligned cylinder layout at constant inlet flow rates does not result in significant difference in reactor performance and it can be neglected. The results provide an indication and optimize performance of reactor; it achieves higher conversion compared with other reforming reactors.

  5. A Highly Efficient Heterogenized Iridium Complex for the Catalytic Hydrogenation of Carbon Dioxide to Formate.

    Science.gov (United States)

    Park, Kwangho; Gunasekar, Gunniya Hariyanandam; Prakash, Natarajan; Jung, Kwang-Deog; Yoon, Sungho

    2015-10-26

    A heterogenized catalyst on a highly porous covalent triazine framework was synthesized and characterized to have a coordination environment similar to that of its homogeneous counterpart. The catalyst efficiently converted CO2 into formate through hydrogenation with a turnover number of 5000 after 2 h and an initial turnover frequency of up to 5300 h(-1) ; both of these values are the highest reported to date for a heterogeneous catalyst, which makes it attractive toward industrial application. Furthermore, the synthesized catalyst was found to be stable in air and was recycled by simple filtration without significant loss of catalytic activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    DEFF Research Database (Denmark)

    Stummann, Magnus Zingler; Høj, Martin; Gabrielsen, Jostein

    Fast pyrolysis of biomass produces a high yield of bio-oil through well-established technologies [1]. To utilizethis oil as liquid fuel the oxygen content must be reduced from 15-30 wt.% down to <1 wt.%, which increases heating value and stability and decreases acidity [1]. Upgrading bio-oil by c......Fast pyrolysis of biomass produces a high yield of bio-oil through well-established technologies [1]. To utilizethis oil as liquid fuel the oxygen content must be reduced from 15-30 wt.% down to ...-oil by catalytic hydrodeoxygenation (HDO) is challenged by severe polymerization and coking upon heating the oil. Alternatively, performing fast pyrolysis in high-pressure hydrogen atmosphere in a fluid bed reactor with a HDO catalyst as bed medium, could immediately stabilize reactive pyrolysis vapors [2...

  7. Thermochemical hydrogen generation of indium oxide thin films

    Directory of Open Access Journals (Sweden)

    Taekyung Lim

    2017-03-01

    Full Text Available Development of alternative energy resources is an urgent requirement to alleviate current energy constraints. As such, hydrogen gas is gaining attention as a future alternative energy source to address existing issues related to limited energy resources and air pollution. In this study, hydrogen generation by a thermochemical water-splitting process using two types of In2O3 thin films was investigated. The two In2O3 thin films prepared by chemical vapor deposition (CVD and sputtering deposition systems contained different numbers of oxygen vacancies, which were directly related to hydrogen generation. The as-grown In2O3 thin film prepared by CVD generated a large amount of hydrogen because of its abundant oxygen vacancies, while that prepared by sputtering had few oxygen vacancies, resulting in low hydrogen generation. Increasing the temperature of the In2O3 thin film in the reaction chamber caused an increase in hydrogen generation. The oxygen-vacancy-rich In2O3 thin film is expected to provide a highly effective production of hydrogen as a sustainable and efficient energy source.

  8. Enhanced hydrogen generation by hydrolysis of Mg doped with flower-like MoS2 for fuel cell applications

    Science.gov (United States)

    Huang, Minghong; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Shao, Huaiyu; Zhu, Min

    2017-10-01

    In this work, flower-like MoS2 spheres are synthesized via a hydrothermal method and the catalytic activity of the as-prepared and bulk MoS2 on hydrolysis of Mg is systematically investigated for the first time. The Mg-MoS2 composites are prepared by ball milling and the hydrogen generation performances of the composites are investigated in 3.5% NaCl solution. The experimental results suggest that the as-prepared MoS2 exhibits better catalytic effect on hydrolysis of Mg compared to bulk MoS2. In particular, Mg-10 wt% MoS2 (as-prepared) composite milled for 1 h shows the best hydrogen generation properties and releases 90.4% of theoretical hydrogen generation capacity within 1 min at room temperature. The excellent catalytic effect of as-prepared MoS2 may be attributed to the following aspects: three-dimensional flower-like MoS2 architectures improve its dispersibility on Mg particles; make the composite more reactive; hamper the generated Mg(OH)2 from adhering to the surface of Mg; and increase the galvanic corrosion of Mg. In addition, a hydrogen generator based on the hydrolysis reaction of Mg-0.2 wt% MoS2 composite is manufactured and it can supply a maximum hydrogen flow rate of 2.5 L/min. The findings here demonstrate the as-prepared flower-like MoS2 can be a promising catalyst for hydrogen generation from Mg.

  9. β-Molybdenum nitride: synthesis mechanism and catalytic response in the gas phase hydrogenation of p-chloronitrobenzene

    NARCIS (Netherlands)

    Cárdenas-Lizana, F.; Gómez-Quero, S.; Perret, N.; Kiwi-Minsker, L.; Keane, M.A.

    2011-01-01

    A temperature programmed treatment of MoO3 in flowing N2 + H2 has been employed to prepare β-phase molybdenum nitride (β-Mo2N) which has been used to promote, for the first time, the catalytic hydrogenation of p-chloronitrobenzene. The reduction/nitridation synthesis steps have been monitored in

  10. In situ catalytic hydrogenation of model compounds and biomass-derived phenolic compounds for bio-oil upgrading

    Science.gov (United States)

    Junfeng Feng; Zhongzhi Yang; Chung-yun Hse; Qiuli Su; Kui Wang; Jianchun Jiang; Junming Xu

    2017-01-01

    The renewable phenolic compounds produced by directional liquefaction of biomass are a mixture of complete fragments decomposed from native lignin. These compounds are unstable and difficult to use directly as biofuel. Here, we report an efficient in situ catalytic hydrogenation method that can convert phenolic compounds into saturated cyclohexanes. The process has...

  11. Catalytic hydrogenation of cyclic carbonates: a practical approach from CO2 and epoxides to methanol and diols.

    Science.gov (United States)

    Han, Zhaobin; Rong, Liangce; Wu, Jiang; Zhang, Lei; Wang, Zheng; Ding, Kuiling

    2012-12-21

    Two birds with one stone: the simultaneous production of two important bulk chemicals, methanol and ethylene glycol, from CO(2) and ethylene oxide has been achieved under mild conditions by the highly efficient homogeneous catalytic hydrogenation of ethylene carbonate in the presence of a (PNP)Ru(II) catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Efficient Electrochemical Hydrogen Peroxide Generation in Water, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — An electrochemical cell is proposed for the efficient generation of 3% hydrogen peroxide (H2O2) in pure water using only power, oxygen and water. H2O2 is an...

  13. Biphasic catalytic conversion of fructose by continuous hydrogenation of HMF over a hydrophobic ruthenium catalyst.

    Science.gov (United States)

    Yang, Yanliang; Du, Zhongtian; Ma, Jiping; Lu, Fang; Zhang, Junjie; Xu, Jie

    2014-05-01

    The production of chemicals directly from sugars is an important step in biomass conversion. Herein, tetrahydro-2,5-furandimethanol (THFDM), obtained from fructose, is formed by using a combination of acid and hydrophobic Ru/SiO2 in a water/cyclohexane biphasic system. Two key factors enable the high selectivity towards THFDM: modifying the hydrogenation catalyst so that it has hydrophobic properties, and the continuous hydrogenation of generated 5-(hydroxymethyl)furfural in the cyclohexane phase. Moreover, the selectivity towards THFDM is found to depend strongly on the acid catalyst used. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Hydrolysis Batteries: Generating Electrical Energy during Hydrogen Absorption.

    Science.gov (United States)

    Xiao, Rui; Chen, Jun; Fu, Kai; Zheng, Xinyao; Wang, Teng; Zheng, Jie; Li, Xingguo

    2018-02-19

    The hydrolysis reaction of aluminum can be decoupled into a battery by pairing an Al foil with a Pd-capped yttrium dihydride (YH 2 -Pd) electrode. This hydrolysis battery generates a voltage around 0.45 V and leads to hydrogen absorption into the YH 2 layer. This represents a new hydrogen absorption mechanism featuring electrical energy generation during hydrogen absorption. The hydrolysis battery converts 8-15 % of the thermal energy of the hydrolysis reaction into usable electrical energy, leading to much higher energy efficiency compared to that of direct hydrolysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Application of microscopy technology in thermo-catalytic methane decomposition to hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Mei, Irene Lock Sow, E-mail: irene.sowmei@gmail.com; Lock, S. S. M., E-mail: serenelock168@gmail.com; Abdullah, Bawadi, E-mail: bawadi-abdullah@petronas.com.my [Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Sri Iskandar, 31750, Perak (Malaysia)

    2015-07-22

    Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production because it produces pure hydrogen without any CO{sub x} emissions. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both specific activity and operational lifetime have been developed. In this work, bimetallic Ni-Pd on gamma alumina support have been developed for methane cracking process by using co-precipitation and incipient wetness impregnation method. The calcined catalysts were characterized to determine their morphologies and physico-chemical properties by using Brunauer-Emmett-Teller method, Field Emission Scanning Electron Microscopy, Energy-dispersive X-ray spectroscopy and Thermogravimetric Analysis. The results suggested that that the catalyst which is prepared by the co-precipitation method exhibits homogeneous morphology, higher surface area, have uniform nickel and palladium dispersion and higher thermal stability as compared to the catalyst which is prepared by wet impregnation method. This characteristics are significant to avoid deactivation of the catalysts due to sintering and carbon deposition during methane cracking process.

  16. Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran and 2-Methyltetrahydrofuran over Bimetallic Copper-Palladium Catalysts.

    Science.gov (United States)

    Chang, Xin; Liu, An-Feng; Cai, Bo; Luo, Jin-Yue; Pan, Hui; Huang, Yao-Bing

    2016-12-08

    The catalytic transfer hydrogenation of furfural to the fuel additives 2-methylfuran (2-MF) and 2-methyltetrahydrofuran (2-MTHF) was investigated over various bimetallic catalysts in the presence of the hydrogen donor 2-propanol. Of all the as-prepared catalysts, bimetallic Cu-Pd catalysts showed the highest catalytic activities towards the formation of 2-MF and 2-MTHF with a total yield of up to 83.9 % yield at 220 °C in 4 h. By modifying the Pd ratios in the Cu-Pd catalyst, 2-MF or 2-MTHF could be obtained selectively as the prevailing product. The other reaction conditions also had a great influence on the product distribution. Mechanistic studies by reaction monitoring and intermediate conversion revealed that the reaction proceeded mainly through the hydrogenation of furfural to furfuryl alcohol, which was followed by deoxygenation to 2-MF in parallel to deoxygenation/ring hydrogenation to 2-MTHF. Finally, the catalyst showed a high reactivity and stability in five catalyst recycling runs, which represents a significant step forward toward the catalytic transfer hydrogenation of furfural. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman

    2018-02-09

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  18. The contrasting catalytic efficiency and cancer cell antiproliferative activity of stereoselective organoruthenium transfer hydrogenation catalysts.

    Science.gov (United States)

    Fu, Ying; Sanchez-Cano, Carlos; Soni, Rina; Romero-Canelon, Isolda; Hearn, Jessica M; Liu, Zhe; Wills, Martin; Sadler, Peter J

    2016-05-28

    The rapidly growing area of catalytic ruthenium chemistry has provided new complexes with potential as organometallic anticancer agents with novel mechanisms of action. Here we report the anticancer activity of four neutral organometallic Ru(II) arene N-tosyl-1,2-diphenylethane-1,2-diamine (TsDPEN) tethered transfer hydrogenation catalysts. The enantiomers (R,R)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8) and (S,S)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8a) exhibited higher potency than cisplatin against A2780 human ovarian cancer cells. When the N-methyl was replaced by N-H, i.e. to give (R,R)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7) and (S,S)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7a), respectively, anticancer activity decreased >5-fold. Their antiproliferative activity appears to be linked to their ability to accumulate in cells, and their mechanism of action might involve inhibition of tubulin polymerisation. This appears to be the first report of the potent anticancer activity of tethered Ru(II) arene complexes, and the structure-activity relationship suggests that the N-methyl substituents are important for potency. In the National Cancer Institute 60-cancer-cell-line screen, complexes 8 and 8a exhibited higher activity than cisplatin towards a broad range of cancer cell lines. Intriguingly, in contrast to their potent anticancer properties, complexes 8/8a are poor catalysts for asymmetric transfer hydrogenation, whereas complexes 7/7a are effective asymmetric hydrogenation catalysts.

  19. Pretreated Landfill Gas Conversion Process via a Catalytic Membrane Reactor for Renewable Combined Fuel Cell-Power Generation

    Directory of Open Access Journals (Sweden)

    Zoe Ziaka

    2013-01-01

    Full Text Available A new landfill gas-based reforming catalytic processing system for the conversion of gaseous hydrocarbons, such as incoming methane to hydrogen and carbon oxide mixtures, is described and analyzed. The exit synthesis gas (syn-gas is fed to power effectively high-temperature fuel cells such as SOFC types for combined efficient electricity generation. The current research work is also referred on the description and design aspects of permreactors (permeable reformers carrying the same type of landfill gas-reforming reactions. Membrane reactors is a new technology that can be applied efficiently in such systems. Membrane reactors seem to perform better than the nonmembrane traditional reactors. The aim of this research includes turnkey system and process development for the landfill-based power generation and fuel cell industries. Also, a discussion of the efficient utilization of landfill and waste type resources for combined green-type/renewable power generation with increased processing capacity and efficiency via fuel cell systems is taking place. Moreover, pollution reduction is an additional design consideration in the current catalytic processors fuel cell cycles.

  20. Catalytic activity of mono and bimetallic Zn/Cu/MWCNTs catalysts for the thermocatalyzed conversion of methane to hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Erdelyi, B. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Institute of Physics, Faculty of Science, P.J. Šafárik University, Park Angelium 9, 040 01 Košice (Slovakia); Oriňak, A., E-mail: andrej.orinak@upjs.sk [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Oriňaková, R. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Lorinčík, J. [Research Center Rez, Hlavní 130, 250 68 Husinec-Řež (Czech Republic); Jerigová, M. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); Velič, D. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); International Laser Centre, Ilkovičová 3, 841 01 Bratislava (Slovakia); Mičušík, M. [Polymer institute, Slovak Academy of Sciences, Dubravská cesta 9, 84541 Bratislava (Slovakia); and others

    2017-02-28

    Highlights: • Zn/Cu/MWCNTs catalyst with good activity. • Methane conversion to hydrogen with high effectivity. • ZnO/Cu responsible for catalytic activity. - Abstract: Mono and bimetallic multiwalled carbon nanotubes (MWCNTs) fortified with Cu and Zn metal particles were studied to improve the efficiency of the thermocatalytic conversion of methane to hydrogen. The surface of the catalyst and the dispersion of the metal particles were studied by scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS) and with energy-dispersive X-ray spectroscopy (EDS). It was confirmed that the metal particles were successfully dispersed on the MWCNT surface and XPS analysis showed that the Zn was oxidised to ZnO at high temperatures. The conversion of methane to hydrogen during the catalytic pyrolysis was studied by pyrolysis gas chromatography using different amounts of catalyst. The best yields of hydrogen were obtained using pyrolysis conditions of 900 °C and 1.2 mg of Zn/Cu/MWCNT catalyst for 1.5 mL of methane.The initial conversion of methane to hydrogen obtained with Zn/Cu/MWCNTs was 49%, which represent a good conversion rate of methane to hydrogen for a non-noble metal catalyst.

  1. Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties

    Science.gov (United States)

    Qu, Yuanju; Pan, Hui; Kwok, Chi Tat

    2016-01-01

    Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs. PMID:27686869

  2. Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN3–Pincer Ligand Containing a Phenanthroline Backbone

    KAUST Repository

    Li, Huaifeng

    2017-05-30

    Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.

  3. Metal-free catalytic oxidation of sulfides to sulfoxides with ammonium nitrate, ammonium hydrogen sulfate and ammonium bromide as catalyst

    OpenAIRE

    Ghorbani-Choghamarani, Arash; Zolfigol, Mohammad Ali; Ayazi-Nasrabadi, Roia

    2010-01-01

    A general and metal-free catalytic oxidation of aliphatic and aromatic sulfides to their corresponding sulfoxides via combination of ammonium nitrate (NH4NO3), supported ammonium hydrogen sulfate on silica gel (NH4HSO4-SiO2) and a catalytic amount of ammonium bromide (NH4Br) in the presence of wet SiO2 (50%, w/w) has been investigated. The reactions were carried out heterogeneously and selectively in short reaction times in CH2Cl2 at room temperature. This protocol is mild and efficient compa...

  4. A study on the hydrogen recombination rates of catalytic recombiners and deliberate ignition

    International Nuclear Information System (INIS)

    Fineschi, F.; Bazzichi, M.; Carcassi, M.

    1994-01-01

    A study is being carried out by the Department of Nuclear and Mechanical Constructions (DCMN) at the University of Pisa on catalytic recombiners and on deliberately induced weak deflagration. The recombination rates of different types of catalytic devices were obtained from a thorough analysis of published experimental data. The main parameter that affects the effectiveness of these devices seems to be the molar density of the deficiency reactant rather than its volumetric concentration. The recombination rate of weak deflagrations in vented compartments has been assessed with experimental tests carried out in a small scale glass vessel. Through a computerized system of analysis of video recordings of the deflagrations, the flame surface and the burned gas volume were obtained as functions of time. Although approximations are inevitable, the method adopted to identify the position of the flame during propagation is more reliable than other non-visual methods (thermocouples and ion-probes). It can only easily be applied to vented weak deflagrations, i.e. when the hydrogen concentration is far from stoichiometric conditions and near to flammability limits, because the pressurization has to be limited due to the low mechanical resistance of the glass. The values of flame surface and burned gas volume were used as inputs for a computer code to calculate the recombining rate, the burning velocity and the pressure transient in the experimental test. The code is being validated with a methodology principally based on a comparison of the measurements of pressure with the calculated values. The research gave some very interesting results on a small scale which should in the future be compared with large scale data

  5. Efficient and selective hydrogen generation from bioethanol using ruthenium pincer-type complexes.

    Science.gov (United States)

    Sponholz, Peter; Mellmann, Dörthe; Cordes, Christoph; Alsabeh, Pamela G; Li, Bin; Li, Yang; Nielsen, Martin; Junge, Henrik; Dixneuf, Pierre; Beller, Matthias

    2014-09-01

    Catalytic generation of hydrogen from aqueous ethanol solution proceeds in the presence of pincer-type transition metal catalysts. Optimal results are obtained applying a [Ru(H)(Cl)(CO)(iPr2PEtN(H)EtPiPr2)] complex (catalyst TON 80,000) in the presence of water and base. This dehydrogenation reaction provides up to 70% acetic acid in a selective manner. For the first time, it is shown that bioethanol obtained from fermentation processes can be used directly in this protocol without the need for water removal. The produced hydrogen can be directly utilized in proton exchange membrane (PEM) fuel cells, since very low amounts of CO are formed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Hydrogen generation from glycerol in batch fermentation process

    Energy Technology Data Exchange (ETDEWEB)

    Seifert, K.; Waligorska, M.; Wojtowski, M.; Laniecki, M. [Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznan (Poland)

    2009-05-15

    The influence of concentration of glycerol, inoculum and total nitrogen on hydrogen generation, in batch dark fermentation process in the presence of digested sludge (at 37 C and at initial pH = 6) was studied. Changes in substrate and products concentrations were modeled with modified Gompertz equations (correlation coefficient R{sup 2} = 0.9015). The 1,3-propandiol, butyric acid, acetic acid, lactic acid and ethanol were found as the main liquid metabolites. Maximal substrate yield for hydrogen was 0.41 mol H{sub 2}/mol glycerol and was obtained for medium containing 10 g/l of glycerol with the lowest amount of inoculum - 1.16 g volatile suspended solid (VSS)/l. Increase of glycerol concentration from 5 to 30 g/l resulted in much better hydrogen generation, namely from 0.345 to 0.715 l H{sub 2}/l. Further increase of glycerol concentration did not cause any changes. The H{sub 2}:CO{sub 2} ratio in biogas in system with the highest substrate yield was always 1. The initial concentration of glycerol does not influence the rate of hydrogen generation. The increase of initial concentration of inoculum from 1.2 to 11.6 g VSS/l results in the decrease of specific hydrogen yield. Nitrogen concentration in medium does not influence the hydrogen production. (author)

  7. Hydrodehalogenation of alkyl iodides with base-mediated hydrogenation and catalytic transfer hydrogenation: application to the asymmetric synthesis of N-protected α-methylamines.

    Science.gov (United States)

    Mandal, Pijus K; Birtwistle, J Sanderson; McMurray, John S

    2014-09-05

    We report a very mild synthesis of N-protected α-methylamines from the corresponding amino acids. Carboxyl groups of amino acids are reduced to iodomethyl groups via hydroxymethyl intermediates. Reductive deiodination to methyl groups is achieved by hydrogenation or catalytic transfer hydrogenation under alkaline conditions. Basic hydrodehalogenation is selective for the iodomethyl group over hydrogenolysis-labile protecting groups, such as benzyloxycarbonyl, benzyl ester, benzyl ether, and 9-fluorenyloxymethyl, thus allowing the conversion of virtually any protected amino acid into the corresponding N-protected α-methylamine.

  8. Catalytic partial oxidation and membrane separation to optimize the conversion of natural gas to syngas and hydrogen.

    Science.gov (United States)

    Capoferri, Daniela; Cucchiella, Barbara; Iaquaniello, Gaetano; Mangiapane, Alessia; Abate, Salvatore; Centi, Gabriele

    2011-12-16

    The multistep integration of hydrogen-selective membranes into catalytic partial oxidation (CPO) technology to convert natural gas into syngas and hydrogen is reported. An open architecture for the membrane reactor is presented, in which coupling of the reaction and hydrogen separation is achieved independently and the required feed conversion is reached through a set of three CPO reactors working at 750, 750 and 920 °C, compared to 1030 °C for conventional CPO technology. Obtaining the same feed conversion at milder operating conditions translates into less natural gas consumption (and CO(2) emissions) and a reduction of variable operative costs of around 10 %. It is also discussed how this energy-efficient process architecture, which is suited particularly to small-to-medium applications, may improve the sustainability of other endothermic, reversible reactions to form hydrogen. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Mixed diphosphine/diamine ruthenium (II) isomers: Synthesis, structural characterization and catalytic hydrogenation of ketones

    Science.gov (United States)

    Nascimento, Rebecca D.; Silva, Andressa K.; Lião, Luciano M.; Deflon, Victor M.; Ueno, Leonardo T.; Dinelli, Luis R.; Bogado, André L.

    2018-01-01

    The complexes trans-[RuCl2(dppb)(cydn)] (1), trans-[RuCl2(dppb)(opda)] (2) and cis-[RuCl2(dppb)(cydn)] (3) were synthesized from [{RuCl2(dppb)}2-μ-(dppb)] {where: dppb = 1,4-bis(diphenylphosphino)butane; cydn = cis and trans (±) 1,2-diaminocyclohexane, and opda = o-phenylenediamine}. The complexes were characterized by nuclear magnetic resonance of phosphorus (31P{1H} NMR), cyclic voltammetry (CV), infrared and ultraviolet/visible spectra (IR and UV/vis) as well as elemental analyses (CHN). The X-ray structures of (1) and (3) were determined and they are presented here. DFT calculations and experimental data showed that the trans isomers are obtained as thermodynamic products while the cis isomers are kinetic products. This behavior is different than described in the literature for similar complexes, where the cis isomer is obtained from the trans isomer. Additionally, the catalytic activity of the complexes (1), (2) and (3) was investigated, as pre-catalysts, in the reduction of the acetophenone and 4-methylacetophenone by transfer-hydrogenation.

  10. Catalytic dry reforming of natural gas for the production of chemicals and hydrogen

    Directory of Open Access Journals (Sweden)

    Verykios Xenophon E.

    2002-01-01

    Full Text Available Carbon dioxide reforming of methane to synthesis gas was studied over Ni-based catalysts. It is shown that, in contrast to other Ni-based catalysts which exhibit continuous deactivation with time-on-stream, the rate over the Ni/La2O3 catalyst increases during the initial 2-3 h of reaction and then tends to be essentially invariable, displaying very good stability. X-ray diffraction, hydrogen and CO uptake studies, as well as high resolution TEM indicate that, under reaction conditions, the Ni particles are partially covered by La2O2CO3 species which are formed by interaction of La2O2 with CO2. Catalytic activity occurs at the Ni- La2O2CO3 interface, while the oxycarbonate species participate directly by reacting with deposited carbon, thus restoring the activity of the Ni sites at the interface. XPS and FTIR studies provide evidence in support of this mechanistic scheme. It was also found that methane cracking on Ni sites and surface reaction between deposited carbon and oxycarbonate species are the rate determining steps in the reaction sequence. A kinetic model is developed based on this mechanistic scheme, which is found to predict satisfactorily the kinetic measurements.

  11. Preparation of Modified Red Mud-Supported Fe Catalysts for Hydrogen Production by Catalytic Methane Decomposition

    Directory of Open Access Journals (Sweden)

    Quanrun Liu

    2017-01-01

    Full Text Available A modified red mud- (MRM- supported Fe catalyst (xFe/MRM was prepared using the homogeneous precipitation method and applied to methane decomposition to produce hydrogen. The TEM and SEM-EDX results suggested that the particle sizes of the xFe/MRM catalysts were much smaller than that of raw red mud (RM, and the active metal Fe was evenly distributed over the catalyst structure. Moreover, BET results indicated that the surface areas and pore volumes of the catalysts were significantly improved, and the pore sizes of xFe/MRM were distributed from 5 to 12 nm, which is typical for a mesoporous material. The activities of those catalysts for the catalytic decomposition of methane were studied at atmospheric pressure at a moderate temperature of 650°C; the results showed that the xFe/MRM catalysts were more active than RM and MRM. The methane conversion curves of xFe/MRM catalysts exhibited similar variation tendencies (three-step during the reaction despite different Fe contents, and the loading amount of Fe clearly affected the activity of the catalysts.

  12. Applications of the water--gas shift reaction. II. Catalytic exchange of deuterium for hydrogen at saturated carbon

    International Nuclear Information System (INIS)

    Laine, R.M.; Thomas, D.W.; Cary, L.W.; Buttrill, S.E.

    1978-01-01

    Previous studies on the homogeneous catalysis of the water-gas shift reaction by metal complexes of groups 6 and 8 had been carried out using aqueous alcoholic solutions of group 8 metal carbonyl complexes made basic with KOH. Substitution of triethylamine (Et 3 N) for KOH as base and alcohol for solvent led to the discovery that Et 3 N in the presence of D 2 O, CO, and Rh 6 (CO) 16 at 150 0 C undergoes an unusual catalytic exchange of deuterium for hydrogen. A suggested mechanism for this reaction is given and includes activation of hydrogen at a saturated carbon

  13. Molecular cobalt pentapyridine catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R; Chang, Christopher J; Sun, Yujie

    2013-11-05

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition including the moiety of the general formula. [(PY5Me.sub.2)CoL].sup.2+, where L can be H.sub.2O, OH.sup.-, a halide, alcohol, ether, amine, and the like. In embodiments of the invention, water, such as tap water or sea water can be subject to low electric potentials, with the result being, among other things, the generation of hydrogen.

  14. Catalytic Ammonia Decomposition over High-Performance Ru/Graphene Nanocomposites for Efficient COx-Free Hydrogen Production

    Directory of Open Access Journals (Sweden)

    Gang Li

    2017-01-01

    Full Text Available Highly-dispersed Ru nanoparticles were grown on graphene nanosheets by simultaneously reducing graphene oxide and Ru ions using ethylene glycol (EG, and the resultant Ru/graphene nanocomposites were applied as a catalyst to ammonia decomposition for COx-free hydrogen production. Tuning the microstructures of Ru/graphene nanocomposites was easily accomplished in terms of Ru particle size, morphology, and loading by adjusting the preparation conditions. This was the key to excellent catalytic activity, because ammonia decomposition over Ru catalysts is structure-sensitive. Our results demonstrated that Ru/graphene prepared using water as a co-solvent greatly enhanced the catalytic performance for ammonia decomposition, due to the significantly improved nano architectures of the composites. The long-term stability of Ru/graphene catalysts was evaluated for COx-free hydrogen production from ammonia at high temperatures, and the structural evolution of the catalysts was investigated during the catalytic reactions. Although there were no obvious changes in the catalytic activities at 450 °C over a duration of 80 h, an aggregation of the Ru nanoparticles was still observed in the nanocomposites, which was ascribed mainly to a sintering effect. However, the performance of the Ru/graphene catalyst was decreased gradually at 500 °C within 20 h, which was ascribed mainly to both the effect of the methanation of the graphene nanosheet under a H2 atmosphere and to enhanced sintering under high temperatures.

  15. Catalytic effect of additional metallic phases on the hydrogen absorption behavior of a Zr-Based alloy

    International Nuclear Information System (INIS)

    Ruiz, F; Peretti, H; Castro, E; Real, S; Visitin, A; Triaca, W

    2005-01-01

    The electrochemical hydrogen absorption of electrodes containing Zr 0 .9Ti 0 .1(Ni 0 .5Mn 0 .25Cr 0 .20V 0 .05) 2 is studied in alkaline media by monitoring the activation and discharge capacity along charge-discharge cycling.The considered alloy is tested in both as melted and annealed condition in order to investigate the catalytic effect of small amounts of micro segregated secondary phases of the Zr-Ni system. Since these catalytic phases are only present in the as melted alloys, tests are also carried out using a composite material elaborated from powders of the annealed alloy with the addition of 18 wt.% of the suspected catalytic phases, melted separately.The hydrogen absorption-desorption behavior for the different cases is discussed and correlated with the metallurgical characterization of the materials.The catalytic effects are studied employing cyclic voltammetry and electrochemical impedance techniques. The results are analyzed in terms of a developed physicochemical model

  16. Development of a low cost, portable solar hydrogen generation device

    Science.gov (United States)

    Rose, Kyle; Aggarwal, M. D.; Batra, Ashok; Wingo, Dennis

    2014-10-01

    Hydrogen is a clean energy source that is environmentally friendly and safe. It is well known that electrolysis is a common method used to produce hydrogen. Other high cost methods for hydrogen production can be countered by the development of this low cost pulse width modulated circuit, using direct current provided by naturally existing solar energy as a power source. Efforts are being made in the scientific community to produce a low cost, portable, solar hydrogen generating device for a number of clean energy applications such as fuel cells and energy storage. Proof of concept has already been tested in the laboratory and a small prototype system is being designed and fabricated in the workshop at Alabama A&M University. Our results of this study and details of the electronic circuit and the prototype are presented.

  17. Development and Improvement of Devices for Hydrogen Generation and Oxidation in Water Detritiation Facility Based on CECE Technology

    International Nuclear Information System (INIS)

    Rozenkevich, M.; Andreev, B.; Magomedbekov, E.; Park, Yu.; Sakharovsky, Yu.; Perevezentsev, A.

    2005-01-01

    Water detritiation facility based on CECE (Combined Electrolysis and Catalytic Exchange) technology needs an electrolyser for water conversion to hydrogen. Use of a conventional alkali electrolyser requires a very deep purification of hydrogen stream from alkali prior to injection to LPCE (Liquid Phase Catalytic Exchange) column. In some applications conversion of detritiated hydrogen back into water is required. This is usually performed via hydrogen catalytic oxidation in a recombiner. This paper presents results of study to improve hydrogen and oxygen purification for alkali electrolysers and develop a hydrogen recombiner based on use of hydrophobic catalyst

  18. Production of dimethylfuran from hydroxymethylfurfural through catalytic transfer hydrogenation with ruthenium supported on carbon.

    Science.gov (United States)

    Jae, Jungho; Zheng, Weiqing; Lobo, Raul F; Vlachos, Dionisios G

    2013-07-01

    RuC ees' transfer: Transfer hydrogenation using alcohols as hydrogen donors and supported ruthenium catalysts results in the selective conversion of hydroxymethylfurfural to dimethylfuran (>80% yield). During transfer hydrogenation, the hydrogen produced from alcohols is utilized in the hydrogenation of hydroxymethylfurfural. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Correlation energy generating potentials for molecular hydrogen

    International Nuclear Information System (INIS)

    Sharma, B.S.; Thakkar, A.J.

    1985-01-01

    A variety of local correlation energy functionals are currently in use. All of them depend, to some extent, on modeling the correlation energy of a homogeneous electron fluid. Since atomic and molecular charge densities are neither uniform nor slowly varying, it is important to attempt to use known high accuracy wave functions to learn about correlation energy functionals appropriate to such systems. We have extended the definition of the correlation energy generating potentials V/sub c/ introduced by Ros. A charge density response to correlation has been allowed for by inclusion of an electron--nuclear component V/sup e/n/sub c/ in addition to the electron--electron component V/sup e/e/sub c/. Two different definitions of V/sup e/n/sub c/ are given. We present the first calculations of V/sub c/ for a molecular system: H 2 . The results show that V/sup e/n/sub c/, in either definition, is by no means negligible. Moreover, V/sup e/e/sub c/ and both forms of V/sup e/n/sub c/ show significant nonlocal dependence on the charge density. Calculations with ten different model correlation energy functionals show that none of them is particularly sensitive to the charge density. However, they are quite sensitive to the parametrization of the electron fluid correlation energy. The schemes which include self-interaction corrections (SIC) are found to be superior to those of Kohn--Sham type. The correlation energy generating potentials implied by the SIC type and empirical correlation energy functionals are found to correspond roughly to averages of one of the accurate potentials

  20. Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation

    Science.gov (United States)

    Wang, Liangbing; Zhang, Wenbo; Zheng, Xusheng; Chen, Yizhen; Wu, Wenlong; Qiu, Jianxiang; Zhao, Xiangchen; Zhao, Xiao; Dai, Yizhou; Zeng, Jie

    2017-11-01

    Hydrogenation of CO2 into fuels and useful chemicals could help to reduce reliance on fossil fuels. Although great progress has been made over the past decades to improve the activity of catalysts for CO2 hydrogenation, more efficient catalysts, especially those based on non-noble metals, are desired. Here we incorporate N atoms into Co nanosheets to boost the catalytic activity toward CO2 hydrogenation. For the hydrogenation of CO2, Co4N nanosheets exhibited a turnover frequency of 25.6 h-1 in a slurry reactor under 32 bar pressure at 150 °C, which was 64 times that of Co nanosheets. The activation energy for Co4N nanosheets was 43.3 kJ mol-1, less than half of that for Co nanosheets. Mechanistic studies revealed that Co4N nanosheets were reconstructed into Co4NHx, wherein the amido-hydrogen atoms directly interacted with the CO2 to form HCOO* intermediates. In addition, the adsorbed H2O* activated amido-hydrogen atoms via the interaction of hydrogen bonds.

  1. Solar photocatalytic generation of hydrogen under ultraviolet-visible ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 33; Issue 1. Solar photocatalytic generation of hydrogen under ultraviolet-visible light irradiation on (CdS/ZnS)/Ag2S + (RuO2/TiO2) photocatalysts. R Priya S Kanmani. Catalysis Volume 33 Issue 1 February 2010 pp 85-88 ...

  2. Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst

    Directory of Open Access Journals (Sweden)

    Hongbin Dai

    2017-02-01

    Full Text Available The synthesis of highly active and selective catalysts is the central issue in the development of hydrous hydrazine (N2H4·H2O as a viable hydrogen carrier. Herein, we report the synthesis of bimetallic Ni-Ir nanocatalyts supported on CeO2 using a one-pot coprecipitation method. A combination of XRD, HRTEM and XPS analyses indicate that the Ni-Ir/CeO2 catalyst is composed of tiny Ni-Ir alloy nanoparticles with an average size of around 4 nm and crystalline CeO2 matrix. The Ni-Ir/CeO2 catalyst exhibits high catalytic activity and excellent selectivity towards hydrogen generation from N2H4·H2O at mild temperatures. Furthermore, in contrast to previously reported Ni-Pt catalysts, the Ni-Ir/CeO2 catalyst shows an alleviated requirement on alkali promoter to achieve its optimal catalytic performance.

  3. Detailed study of the plasma-activated catalytic generation of ammonia in N2-H2 plasmas

    Science.gov (United States)

    van Helden, J. H.; Wagemans, W.; Yagci, G.; Zijlmans, R. A. B.; Schram, D. C.; Engeln, R.; Lombardi, G.; Stancu, G. D.; Röpcke, J.

    2007-02-01

    We investigated the efficiency and formation mechanism of ammonia generation in recombining plasmas generated from mixtures of N2 and H2 under various plasma conditions. In contrast to the Haber-Bosch process, in which the molecules are dissociated on a catalytic surface, under these plasma conditions the precursor molecules, N2 and H2, are already dissociated in the gas phase. Surfaces are thus exposed to large fluxes of atomic N and H radicals. The ammonia production turns out to be strongly dependent on the fluxes of atomic N and H radicals to the surface. By optimizing the atomic N and H fluxes to the surface using an atomic nitrogen and hydrogen source ammonia can be formed efficiently, i.e., more than 10% of the total background pressure is measured to be ammonia. The results obtained show a strong similarity with results reported in literature, which were explained by the production of ammonia at the surface by stepwise addition reactions between adsorbed nitrogen and hydrogen containing radicals at the surface and incoming N and H containing radicals. Furthermore, our results indicate that the ammonia production is independent of wall material. The high fluxes of N and H radicals in our experiments result in a passivated surface, and the actual chemistry, leading to the formation of ammonia, takes place in an additional layer on top of this passivated surface.

  4. PANI/NaTaO3 composite photocatalyst for enhanced hydrogen generation under UV light irradiation

    Directory of Open Access Journals (Sweden)

    Zielińska Beata

    2017-09-01

    Full Text Available A PANI/NaTaO3 composite was successfully synthesized by an oxidative polymerization of aniline monomer in hydrochloric acid solution containing sodium tantalate. NaTaO3 at a monoclinic structure was produced via hydrothermal method. The photocatalytic activities of the unmodified NaTaO3 and PANI/NaTaO3 were evaluated for hydrogen generation from an aqueous HCOOH solution and under UV light irradiation. The results showed that the evolution rate of H2 increased significantly when NaTaO3 was modified with PANI. The enhancement of the photocatalytic activity of PANI/NaTaO3 composite was ascribed to the effective charge transfer and separation between NaTaO3 and PANI, which reduced their recombination. This indicates that PANI modification of tantalate photocatalysts may open up a new way to prepare highly efficient catalytic materials for H2 generation.

  5. Pt nanoparticles modified by rare earth oxides: Electronic effect and influence to catalytic hydrogenation of 3-phenoxybenzaldehyde

    International Nuclear Information System (INIS)

    Mou, Zhigang; Han, Ming; Li, Gang; Du, Yukou; Yang, Ping; Zhang, Hailu; Deng, Zongwu

    2013-01-01

    Graphical abstract: - Highlights: • The rare earths modified Pt/Al 2 O 3 were prepared by colloidal deposition method. • Modification of Pt by the rare earth enhanced catalytic hydrogenation activity. • The activity improvement is due to electron interaction between Pt and rare earth. • The hydrogenation mechanism of rare earth modified Pt catalyst was proposed. - Abstract: The rare earth elements (La, Ce, Nd, Sm, Pr, and Gd) modified Pt/Al 2 O 3 catalysts were prepared by the colloidal deposition and chemical reduction methods, respectively. Pt nanoparticles with average size 3 ± 0.5 nm were uniformly dispersed on the surface of Al 2 O 3 for the samples prepared by the colloidal deposition method, which exhibited higher activities in the hydrogenation of 3-phenoxybenzadehyde than the corresponding samples prepared by chemical reduction method. Moreover, except Gd, the catalysts modified by rare earth elements showed better catalytic performance than unmodified Pt/Al 2 O 3 . For Pt–Ce/Al 2 O 3 catalyst, when the weight percent of Pt and Ce was 0.5 and 0.25, respectively, the hydrogenation conversion of 3-phenoxybenzaldehyde was 97.3% after 6 h reaction. This activity improvement is due to the electronic interaction between Pt and rare earth elements, which was investigated by X-ray photoelectron spectroscopy

  6. Pt nanoparticles modified by rare earth oxides: Electronic effect and influence to catalytic hydrogenation of 3-phenoxybenzaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Mou, Zhigang; Han, Ming; Li, Gang; Du, Yukou [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Yang, Ping, E-mail: pyang@suda.edu.cn [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Zhang, Hailu [Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215123 (China); Deng, Zongwu, E-mail: zwdeng2007@sinano.ac.cn [Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215123 (China)

    2013-11-15

    Graphical abstract: - Highlights: • The rare earths modified Pt/Al{sub 2}O{sub 3} were prepared by colloidal deposition method. • Modification of Pt by the rare earth enhanced catalytic hydrogenation activity. • The activity improvement is due to electron interaction between Pt and rare earth. • The hydrogenation mechanism of rare earth modified Pt catalyst was proposed. - Abstract: The rare earth elements (La, Ce, Nd, Sm, Pr, and Gd) modified Pt/Al{sub 2}O{sub 3} catalysts were prepared by the colloidal deposition and chemical reduction methods, respectively. Pt nanoparticles with average size 3 ± 0.5 nm were uniformly dispersed on the surface of Al{sub 2}O{sub 3} for the samples prepared by the colloidal deposition method, which exhibited higher activities in the hydrogenation of 3-phenoxybenzadehyde than the corresponding samples prepared by chemical reduction method. Moreover, except Gd, the catalysts modified by rare earth elements showed better catalytic performance than unmodified Pt/Al{sub 2}O{sub 3}. For Pt–Ce/Al{sub 2}O{sub 3} catalyst, when the weight percent of Pt and Ce was 0.5 and 0.25, respectively, the hydrogenation conversion of 3-phenoxybenzaldehyde was 97.3% after 6 h reaction. This activity improvement is due to the electronic interaction between Pt and rare earth elements, which was investigated by X-ray photoelectron spectroscopy.

  7. Dibenzothiophene hydrodesulfurization over Ru promoted alumina based catalysts using in situ generated hydrogen

    International Nuclear Information System (INIS)

    Muhammad, Yaseen; Lu Yingzhou; Shen Chong; Li Chunxi

    2011-01-01

    Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-400 o C using in situ generated hydrogen coupled with the effect of selected organic additives for the first time. Four kinds of alumina based catalysts i.e. Co-Mo/Al 2 O 3 , Ni-Mo/Al 2 O 3 , Ru-Co-Mo/Al 2 O 3 and Ru-Ni-Mo/Al 2 O 3 were used for the desulfurization process, which were prepared following incipient impregnation method with fixed metal loadings (wt.%) of Co, Ni, Mo and Ru. The surface area, average pore diameter and pore volume distribution of the fresh and used catalysts were measured by N 2 adsorption using BET method. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Addition and mutual reaction of specific quantities of water and ethanol provided the necessary in situ hydrogen for the desulfurization reaction. Organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine did impinge the HDS activity of the catalysts in different ways. Liquid samples from reaction products were quantitatively analyzed by HPLC technique while qualitative analyses were made using GC-MS. Both of these techniques showed that Ni-based catalysts were more active than Co-based ones at all conditions. Moreover, incorporation of Ru to both Co and Ni-based catalysts greatly promoted desulfurization activity of these catalysts. DBT conversion of up to 84% was achieved with Ru-Ni-Mo/Al 2 O 3 catalyst at 380 o C temperature for 11 h. Catalyst systems followed the HDS activity order as: Ru-Ni-Mo/Al 2 O 3 > Ni-Mo/Al 2 O 3 > Ru-Co-Mo/Al 2 O 3 > Co-Mo/Al 2 O 3 at all conditions. Cost effectiveness, mild operating conditions and reasonably high catalytic activity using in situ generated hydrogen mechanism proved our process to be useful for HDS of DBT.

  8. Dibenzothiophene hydrodesulfurization over Ru promoted alumina based catalysts using in situ generated hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Muhammad, Yaseen; Shen, Chong; Li, Chunxi [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Lu, Yingzhou [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

    2011-02-15

    Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-400 C using in situ generated hydrogen coupled with the effect of selected organic additives for the first time. Four kinds of alumina based catalysts i.e. Co-Mo/Al{sub 2}O{sub 3}, Ni-Mo/Al{sub 2}O{sub 3}, Ru-Co-Mo/Al{sub 2}O{sub 3} and Ru-Ni-Mo/Al{sub 2}O{sub 3} were used for the desulfurization process, which were prepared following incipient impregnation method with fixed metal loadings (wt.%) of Co, Ni, Mo and Ru. The surface area, average pore diameter and pore volume distribution of the fresh and used catalysts were measured by N{sub 2} adsorption using BET method. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Addition and mutual reaction of specific quantities of water and ethanol provided the necessary in situ hydrogen for the desulfurization reaction. Organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine did impinge the HDS activity of the catalysts in different ways. Liquid samples from reaction products were quantitatively analyzed by HPLC technique while qualitative analyses were made using GC-MS. Both of these techniques showed that Ni-based catalysts were more active than Co-based ones at all conditions. Moreover, incorporation of Ru to both Co and Ni-based catalysts greatly promoted desulfurization activity of these catalysts. DBT conversion of up to 84% was achieved with Ru-Ni-Mo/Al{sub 2}O{sub 3} catalyst at 380 C temperature for 11 h. Catalyst systems followed the HDS activity order as: Ru-Ni-Mo/Al{sub 2}O{sub 3}> Ni-Mo/Al{sub 2}O{sub 3}> Ru-Co-Mo/Al{sub 2}O{sub 3}> Co-Mo/Al{sub 2}O{sub 3} at all conditions. Cost effectiveness, mild operating conditions and reasonably high catalytic activity using in situ generated hydrogen mechanism proved our process to be useful for HDS of DBT. (author)

  9. Energy Efficient Catalytic Activation of Hydrogen peroxide for Green Chemical Processes: Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Collins, Terrence J.; Horwitz, Colin

    2004-11-12

    A new, highly energy efficient approach for using catalytic oxidation chemistry in multiple fields of technology has been pursued. The new catalysts, called TAML® activators, catalyze the reactions of hydrogen peroxide and other oxidants for the exceptionally rapid decontamination of noninfectious simulants (B. atrophaeus) of anthrax spores, for the energy efficient decontamination of thiophosphate pesticides, for the facile, low temperature removal of color and organochlorines from pulp and paper mill effluent, for the bleaching of dyes from textile mill effluents, and for the removal of recalcitrant dibenzothiophene compounds from diesel and gasoline fuels. Highlights include the following: 1) A 7-log kill of Bacillus atrophaeus spores has been achieved unambiguously in water under ambient conditions within 15 minutes. 2) The rapid total degradation under ambient conditions of four thiophosphate pesticides and phosphonate degradation intermediates has been achieved on treatment with TAML/peroxide, opening up potential applications of the decontamination system for phosphonate structured chemical warfare agents, for inexpensive, easy to perform degradation of stored and aged pesticide stocks (especially in Africa and Asia), for remediation of polluted sites and water bodies, and for the destruction of chemical warfare agent stockpiles. 3) A mill trial conducted in a Pennsylvanian bleached kraft pulp mill has established that TAML catalyst injected into an alkaline peroxide bleach tower can significantly lower color from the effluent stream promising a new, more cost effective, energy-saving approach for color remediation adding further evidence of the value and diverse engineering capacity of the approach to other field trials conducted on effluent streams as they exit the bleach plant. 4) Dibenzothiophenes (DBTs), including 4,6-dimethyldibenzothiophene, the most recalcitrant sulfur compounds in diesel and gasoline, can be completely removed from model gasoline

  10. A review of recent advances on the effects of microstructural refinement and nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Varin, R. A.; Zbroniec, L. [University of Waterloo, Department of Mechanical and Mechatronics Engineering, Waterloo, Ontario (Canada); Polanski, M.; Bystrzycki, J. [Faculty of Advanced Technology and Chemistry, Military University of Technology, Warsaw (Poland)

    2011-07-01

    The recent advances on the effects of microstructural refinement and various nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides obtained in the last few years in the allied laboratories at the University of Waterloo (Canada) and Military University of Technology (Warsaw, Poland) are critically reviewed in this paper. The research results indicate that microstructural refinement (particle and grain size) induced by ball milling influences quite modestly the hydrogen storage properties of simple metal and complex metal hydrides. On the other hand, the addition of nanometric elemental metals acting as potent catalysts and/or metal halide catalytic precursors brings about profound improvements in the hydrogen absorption/desorption kinetics for simple metal and complex metal hydrides alike. In general, catalytic precursors react with the hydride matrix forming a metal salt and free nanometric or amorphous elemental metals/intermetallics which, in turn, act catalytically. However, these catalysts change only kinetic properties i.e. the hydrogen absorption/desorption rate but they do not change thermodynamics (e.g., enthalpy change of hydrogen sorption reactions). It is shown that a complex metal hydride, LiAlH{sub 4}, after high energy ball milling with a nanometric Ni metal catalyst and/or MnCl{sub 2} catalytic precursor, is able to desorb relatively large quantities of hydrogen at room temperature, 40 and 80 {sup o}C. This kind of behavior is very encouraging for the future development of solid state hydrogen systems. (authors)

  11. Hydrogen generation utilizing integrated CO2 removal with steam reforming

    Science.gov (United States)

    Duraiswamy, Kandaswamy; Chellappa, Anand S

    2013-07-23

    A steam reformer may comprise fluid inlet and outlet connections and have a substantially cylindrical geometry divided into reforming segments and reforming compartments extending longitudinally within the reformer, each being in fluid communication. With the fluid inlets and outlets. Further, methods for generating hydrogen may comprise steam reformation and material adsorption in one operation followed by regeneration of adsorbers in another operation. Cathode off-gas from a fuel cell may be used to regenerate and sweep the adsorbers, and the operations may cycle among a plurality of adsorption enhanced reformers to provide a continuous flow of hydrogen.

  12. Monitoring of hydrogen generated by corrosion reactions of steel

    Energy Technology Data Exchange (ETDEWEB)

    Abbassi, A.; Mihi, A.; Benbouta, R. [Corrosion Laboratory, Department of Mechanical Engineering, Faculty of Engineering Science, University of Batna, 05000 Batna (Algeria)

    2008-12-15

    A solid-state sensor has been constructed and used for the detection of hydrogen generated during corrosion of steel in pH2 solutions. In addition to that, weight loss, AC impedance measurements and selected slow strain rate tests were performed under the same conditions as the hydrogen measurements in order to ascertain the degree of embrittlement of steel. The use of such a device in cathodic protection by impressed current in artificial seawater was also investigated. (Abstract Copyright [2008], Wiley Periodicals, Inc.)

  13. Perspectives for generation companies and the emerging hydrogen economy

    International Nuclear Information System (INIS)

    Cowan, N.

    2004-01-01

    'Full text:' Canadian and global power generation supply is evolving towards inclusion of emerging types of technologies for electricity production. Although much of Canadian electricity supply will continue to be derived from traditional sources in the foreseeable future the band for capital cost competitiveness is narrowing between the once clear-cut technological winners and emerging generation technologies creating opportunity for new technologies to commercialize in the market. OPG has been active in the development and commercialization of stationary high temperature fuel cells for several years. The major activity has been a partnering initiative to engineer and implement Solid Oxide Fuel Cell (SOFC) demonstration installations. The relationship with SOFC developer Siemens-Westinghouse out of Pittsburgh has allowed OPG to maintain an ongoing involvement in the emerging fuel cell industry, while exploring the broader implications of this technology for the power industry business model. OPG is part of the 'Hydrogen Village Partnership'. The Hydrogen Village will demonstrate and deploy various hydrogen production, storage and delivery techniques as well as applications of hydrogen such as fuel cells for stationary, transportation (mobile) and portable applications. OPG maintains an active role in the demonstration of emerging technologies for a number of reasons: 1) advancing commercialization of emerging generation technologies, 2) 'hands-on' participation in the deployment of such technology in order to gather and apply market knowledge 3) Involvement in developing technology as a part of commitment to sustainable development. (author)

  14. Effect of Co crystallinity on Co/CNT catalytic activity in CO/CO{sub 2} hydrogenation and CO disproportionation

    Energy Technology Data Exchange (ETDEWEB)

    Chernyak, Sergei A., E-mail: chernyak.msu@gmail.com [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation); Suslova, Evgeniya V.; Egorov, Alexander V.; Maslakov, Konstantin I. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Savilov, Serguei V.; Lunin, Valery V. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation)

    2016-05-30

    Highlights: • Amorphous and crystalline Co supported on CNTs were obtained by tuning of CNT surface. • CO and CO{sub 2} hydrogenation does not occur on amorphous Co particles. • Thermal activation of amorphous Co led to crystallization of metal. • Amorphous Co promotes CO disproportionation. • Carbon shells around the amorphous metal particles after the CO hydrogenation. - Abstract: Carbon nanotubes (CNTs) with different degree of surface oxidation were used as supports for 5 wt.% Co catalysts. CNTs and Co/CNT catalysts were analyzed by XPS, nitrogen adsorption, TEM and electron diffraction to reveal their structure. High oxidation degree of CNT surface (8.6 at.% of O) and low Co loading led to predominantly amorphous Co species. This resulted in the absence of catalytic activity in both CO and CO{sub 2} hydrogenation in opposite to the catalyst supported on less oxidized CNTs (5.4 at.% of O) where Co species were found to be crystalline. Thermal treatment of inactive catalyst in H{sub 2} and He led to the formation of Co crystal phase which was active in catalysis. Co particle size in catalyst supported on strongly oxidized CNTs was unchanged during CO hydrogenation in opposite to Co supported on less oxidized CNTs. Carbon shell formation on the surface of amorphous Co particles during CO hydrogenation was revealed, which testified CO disproportionation. Qualitative mechanism of CO hydrogenation on small Co particles was proposed.

  15. Solar powered hydrogen generating facility and hydrogen powered vehicle fleet. Final technical report, August 11, 1994--January 6, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Provenzano, J.J.

    1997-04-01

    This final report describes activities carried out in support of a demonstration of a hydrogen powered vehicle fleet and construction of a solar powered hydrogen generation system. The hydrogen generation system was permitted for construction, constructed, and permitted for operation. It is not connected to the utility grid, either for electrolytic generation of hydrogen or for compression of the gas. Operation results from ideal and cloudy days are presented. The report also describes the achievement of licensing permits for their hydrogen powered trucks in California, safety assessments of the trucks, performance data, and information on emissions measurements which demonstrate performance better than the Ultra-Low Emission Vehicle levels.

  16. Molecular hydrogen and catalytic combustion in the production of hyperpolarized 83Kr and 129Xe MRI contrast agents.

    Science.gov (United States)

    Rogers, Nicola J; Hill-Casey, Fraser; Stupic, Karl F; Six, Joseph S; Lesbats, Clémentine; Rigby, Sean P; Fraissard, Jacques; Pavlovskaya, Galina E; Meersmann, Thomas

    2016-03-22

    Hyperpolarized (hp) (83)Kr is a promising MRI contrast agent for the diagnosis of pulmonary diseases affecting the surface of the respiratory zone. However, the distinct physical properties of (83)Kr that enable unique MRI contrast also complicate the production of hp (83)Kr. This work presents a previously unexplored approach in the generation of hp (83)Kr that can likewise be used for the production of hp (129)Xe. Molecular nitrogen, typically used as buffer gas in spin-exchange optical pumping (SEOP), was replaced by molecular hydrogen without penalty for the achievable hyperpolarization. In this particular study, the highest obtained nuclear spin polarizations were P =29% for(83)Kr and P= 63% for (129)Xe. The results were reproduced over many SEOP cycles despite the laser-induced on-resonance formation of rubidium hydride (RbH). Following SEOP, the H2 was reactively removed via catalytic combustion without measurable losses in hyperpolarized spin state of either (83)Kr or (129)Xe. Highly spin-polarized (83)Kr can now be purified for the first time, to our knowledge, to provide high signal intensity for the advancement of in vivo hp (83)Kr MRI. More generally, a chemical reaction appears as a viable alternative to the cryogenic separation process, the primary purification method of hp(129)Xe for the past 2 1/2 decades. The inherent simplicity of the combustion process will facilitate hp (129)Xe production and should allow for on-demand continuous flow of purified and highly spin-polarized (129)Xe.

  17. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni2P supported on active carbon

    Science.gov (United States)

    Xu, Yanli; Sang, Huanxin; Wang, Kang; Wang, Xitao

    2014-10-01

    In this article, an environmentally friendly non-noble-metal class of Cs-Ni2P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H2-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni2P particles, which decreases the strength of Nisbnd C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni2P/AC catalysts display much higher catalytic performance as compared to Ni2P/AC catalyst. Cs-Ni2P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni2P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

  18. Sensitivity analyses on in-vessel hydrogen generation for KNGR

    International Nuclear Information System (INIS)

    Kim, See Darl; Park, S.Y.; Park, S.H.; Park, J.H.

    2001-03-01

    Sensitivity analyses for the in-vessel hydrogen generation, using the MELCOR program, are described in this report for the Korean Next Generation Reactor. The typical accident sequences of a station blackout and a large LOCA scenario are selected. A lower head failure model, a Zircaloy oxidation reaction model and a B 4 C reaction model are considered for the sensitivity parameters. As for the base case, 1273.15K for a failure temperature of the penetrations or the lower head, an Urbanic-Heidrich correlation for the Zircaloy oxidation reaction model and the B 4 C reaction model are used. Case 1 used 1650K as the failure temperature for the penetrations and Case 2 considered creep rupture instead of penetration failure. Case 3 used a MATPRO-EG and G correlation for the Zircaloy oxidation reaction model and Case 4 turned off the B 4 C reaction model. The results of the studies are summarized below : (1) When the penetration failure temperature is higher, or the creep rupture failure model is considered, the amount of hydrogen increases for two sequences. (2) When the MATPRO-EG and G correlation for a Zircaloy oxidation reaction is considered, the amount of hydrogen is less than the Urbanic-Heidrich correlation (Base case) for both scenarios. (3) When the B 4 C reaction model turns off, the amount of hydrogen decreases for two sequences

  19. Preparation of Cu-Fe-Al-O nanosheets and their catalytic application in methanol steam reforming for hydrogen production

    Science.gov (United States)

    Wang, Leilei; Zhang, Fan; Miao, Dinghao; Zhang, Lei; Ren, Tiezhen; Hui, Xidong; He, Zhanbing

    2017-03-01

    Candidates of precious metal catalysts, prepared in a facile and environmental way and showing high catalytic performances at low temperatures, are always highly desired by industry. In this work, large-scale Cu-Fe-Al-O nanosheets were synthesized by facile dealloying of Al-Cu-Fe alloys in NaOH solution. The composition, microscopic morphology, and crystal structure were respectively investigated using wavelength-dispersive x-ray spectroscopy with an electron probe microanalyzer, scanning electron microscopy, x-ray diffraction, and transmission electron microscopy. Furthermore, we found that the 2D Cu-Fe-Al-O nanosheets gave excellent catalytic performances in hydrogen production by methanol steam reforming at relatively low temperatures, e.g. 513 K.

  20. Utilization of Aluminum Waste with Hydrogen and Heat Generation

    Science.gov (United States)

    Buryakovskaya, O. A.; Meshkov, E. A.; Vlaskin, M. S.; Shkolnokov, E. I.; Zhuk, A. Z.

    2017-10-01

    A concept of energy generation via hydrogen and heat production from aluminum containing wastes is proposed. The hydrogen obtained by oxidation reaction between aluminum waste and aqueous solutions can be supplied to fuel cells and/or infrared heaters for electricity or heat generation in the region of waste recycling. The heat released during the reaction also can be effectively used. The proposed method of aluminum waste recycling may represent a promising and cost-effective solution in cases when waste transportation to recycling plants involves significant financial losses (e.g. remote areas). Experiments with mechanically dispersed aluminum cans demonstrated that the reaction rate in alkaline solution is high enough for practical use of the oxidation process. In theexperiments aluminum oxidation proceeds without any additional aluminum activation.

  1. Thermo-Catalytic Methane Decomposition for Hydrogen Production: Effect of Palladium Promoter on Ni-based Catalysts

    Directory of Open Access Journals (Sweden)

    Irene Lock Sow Mei

    2016-08-01

    Full Text Available Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both catalytic activity and operational lifetime have been developed. In this study, the effect of palladium (Pd as a promoter onto Ni supported on alumina catalyst has been investigated by using co-precipitation technique. The introduction of Pd promotes better catalytic activity, operational lifetime and thermal stability of the catalyst. As expected, highest methane conversion was achieved at reaction temperature of 800 °C while the bimetallic catalyst (1 wt.% Ni -1wt.% Pd/Al2O3 gave the highest methane conversion of 70% over 15 min of time-on-stream (TOS. Interestingly, the introduction of Pd as promoter onto Ni-based catalyst also has a positive effect on the operational lifetime and thermal stability of the catalyst as the methane conversion has improved significantly over 240 min of TOS. Copyright © 2016 BCREC GROUP. All rights reserved Received: 21st January 2016; Revised: 6th February 2016; Accepted: 6th March 2016 How to Cite: Mei, I.L.S., Lock, S.S.M., Vo, D.V.N., Abdullah, B. (2016. Thermo-Catalytic Methane Decomposition for Hydrogen Production: Effect of Palladium Promoter on Ni-based Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 191-199 (doi:10.9767/bcrec.11.2.550.191-199 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.550.191-199

  2. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane; Reduction catalytique selective des oxydes d'azote (NO{sub x}) provenant d'effluents gazeux industriels par l'hydrogene ou le methane

    Energy Technology Data Exchange (ETDEWEB)

    Engelmann Pirez, M

    2004-12-15

    This work deals with the selective catalytic reduction of nitrogen oxides (NO{sub x}), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N{sub 2}, in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO{sub 3}, on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  3. Mechanistic studies of catalytic hydrogenation: gas tritiation and deuteration of 2-acetamidoacrylic acid and alpha-acetamidocinnamic acid

    International Nuclear Information System (INIS)

    Tang, Y.S.; Morimoto, H.; Un, S.; Rapoport, H.

    1986-01-01

    The difference of labeling in heterogeneous catalytic gas tritiations of 2-acetamidocinnamic acid and 2-acetamidoacrylic acid is demonstrated by 3 H NMR spectroscopy. The nonequivalent addition of tritium to the double bond of 2-acetamidoacrylic acid is due to simultaneous hydrogen-tritium exchange during adsorption on the catalyst surface. A new mechanistic interpretation has been proposed to explain the behavior of this substrate. These conclusions were substantiated by mass spectrometry results obtained using D 2 and deuterated solvents. Steric effects on vinylic exchange studied by GLRC were also reported. 2 refs.; 6 figs.; 3 tabs

  4. DWPF Hydrogen Generation Study-Form of Noble Metal SRAT Testing

    Energy Technology Data Exchange (ETDEWEB)

    Bannochie, C

    2005-09-01

    The Defense Waste Processing Facility, DWPF, has requested that the Savannah River National Laboratory, SRNL, investigate the factors that contribute to hydrogen generation to determine if current conservatism in setting the DWPF processing window can be reduced. A phased program has been undertaken to increase understanding of the factors that influence hydrogen generation in the DWPF Chemical Process Cell, CPC. The hydrogen generation in the CPC is primarily due to noble metal catalyzed decomposition of formic acid with a minor contribution from radiolytic processes. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Two sludge simulants were obtained, one with co-precipitated noble metals and one without noble metals. Co-precipitated noble metals were expected to better match real waste behavior than using trimmed noble metals during CPC simulations. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The two original and two heat-treated sludge simulants were then used as feeds to Sludge Receipt and Adjustment Tank, SRAT, process simulations. Testing was done at relatively high acid stoichiometries, {approx}175%, and without mercury in order to ensure significant hydrogen generation. Hydrogen generation rates were monitored during processing to assess the impact of the form of noble metals. The following observations were made on the data: (1) Co-precipitated noble metal simulant processed similarly to trimmed noble metal simulant in most respects, such as nitrite to nitrate conversion, formate destruction, and pH, but differently with respect to hydrogen generation: (A

  5. Ruthenium(0) nanoclusters stabilized by a Nanozeolite framework: isolable, reusable, and green catalyst for the hydrogenation of neat aromatics under mild conditions with the unprecedented catalytic activity and lifetime.

    Science.gov (United States)

    Zahmakiran, Mehmet; Tonbul, Yalçin; Ozkar, Saim

    2010-05-12

    The hydrogenation of aromatics is a ubiquitous chemical transformation used in both the petrochemical and specialty industry and is important for the generation of clean diesel fuels. Reported herein is the discovery of a superior heterogeneous catalyst, superior in terms of catalytic activity, selectivity, and lifetime in the hydrogenation of aromatics in the solvent-free system under mild conditions (at 25 degrees C and 42 +/- 1 psig initial H(2) pressure). Ruthenium(0) nanoclusters stabilized by a nanozeolite framework as a new catalytic material is reproducibly prepared from the borohydride reduction of a colloidal solution of ruthenium(III)-exchanged nanozeolites at room temperature and characterized by using ICP-OES, XRD, XPS, DLS, TEM, HRTEM, TEM/EDX, mid-IR, far-IR, and Raman spectroscopy. The resultant ruthenium(0) nanoclusters hydrogenate neat benzene to cyclohexane with 100% conversion under mild conditions (at 25 degrees C and 42 +/- 1 psig initial H(2) pressure) with record catalytic activity (initial TOF = 5430 h(-1)) and lifetime (TTO = 177 200). They provide exceptional catalytic activity not only in the hydrogenation of neat benzene but also in the solvent-free hydrogenation of methyl substituted aromatics such as toluene, o-xylene, and mesitylene under otherwise identical conditions. Moreover, they are an isolable, bottleable, and reusable catalyst in the hydrogenation of neat aromatics. When the isolated ruthenium(0) nanoclusters are reused, they retain 92% of their initial catalytic activity even for the third run in the hydrogenation of neat benzene under the same conditions as those of the first run. The work reported here also includes (i) far-infrared spectroscopic investigation of nanozeolite, ruthenium(III)-exchanged-nanozeolite, and ruthenium(0) nanoclusters stabilized by a nanozeolite framework, indicating that the host framework remains intact after the formation of a nanozeolite framework stabilized ruthenium(0) nanoclusters; (ii) the

  6. Catalytic Glycerol Hydrodeoxygenation under Inert Atmosphere: Ethanol as a Hydrogen Donor

    Directory of Open Access Journals (Sweden)

    Efterpi S. Vasiliadou

    2014-12-01

    Full Text Available Glycerol hydrodeoxygenation to 1,2-propanediol (1,2-PDO is a reaction of high interest. However, the need for hydrogen supply is a main drawback of the process. According to the concept investigated here, 1,2-propanediol is efficiently formed using bio-glycerol feedstock with H2 formed in situ via ethanol aqueous phase reforming. Ethanol is thought to be a promising H2 source, as it is alcohol that can be used instead of methanol for transesterification of oils and fats. The H2 generated is consumed in the tandem reaction of glycerol hydrodeoxygenation. The reaction cycle proceeds in liquid phase at 220–250 °C and 1.5–3.5 MPa initial N2 pressure for a 2 and 4-h reaction time. Pt-, Ni- and Cu-based catalysts have been synthesized, characterized and evaluated in the reaction. Among the materials tested, Pt/Fe2O3-Al2O3 exhibited the most promising performance in terms of 1,2-propanediol productivity, while reusability tests showed a stable behavior. Structural integrity and no formation of carbonaceous deposits were verified via Temperature Programmed Desorption of hydrogen (TPD-H2 and thermogravimetric analysis of the fresh and used Pt/FeAl catalyst. A study on the effect of various operating conditions (reaction time, temperature and pressure indicated that in order to maximize 1,2-propanediol productivity and yield, milder reaction conditions should be applied. The highest 1,2-propanediol yield, 53% (1.1 g1,2-PDO gcat−1·h−1, was achieved at a lower reaction temperature of 220 °C.

  7. HIGH EFFICIENCY GENERATION OF HYDROGEN FUELS USING NUCLEAR POWER

    Energy Technology Data Exchange (ETDEWEB)

    BROWN,LC; BESENBRUCH,GE; LENTSCH,RD; SCHULTZ,KR; FUNK,JF; PICKARD,PS; MARSHALL,AC; SHOWALTER,SK

    2003-06-01

    OAK B202 HIGH EFFICIENCY GENERATION OF HYDROGEN FUELS USING NUCLEAR POWER. Combustion of fossil fuels, used to power transportation, generate electricity, heat homes and fuel industry provides 86% of the world's energy. Drawbacks to fossil fuel utilization include limited supply, pollution, and carbon dioxide emissions. Carbon dioxide emissions, thought to be responsible for global warming, are now the subject of international treaties. Together, these drawbacks argue for the replacement of fossil fuels with a less-polluting potentially renewable primary energy such as nuclear energy. Conventional nuclear plants readily generate electric power but fossil fuels are firmly entrenched in the transportation sector. Hydrogen is an environmentally attractive transportation fuel that has the potential to displace fossil fuels. Hydrogen will be particularly advantageous when coupled with fuel cells. Fuel cells have higher efficiency than conventional battery/internal combustion engine combinations and do not produce nitrogen oxides during low-temperature operation. Contemporary hydrogen production is primarily based on fossil fuels and most specifically on natural gas. When hydrogen is produced using energy derived from fossil fuels, there is little or no environmental advantage. There is currently no large scale, cost-effective, environmentally attractive hydrogen production process available for commercialization, nor has such a process been identified. The objective of this work is to find an economically feasible process for the production of hydrogen, by nuclear means, using an advanced high-temperature nuclear reactor as the primary energy source. Hydrogen production by thermochemical water-splitting (Appendix A), a chemical process that accomplishes the decomposition of water into hydrogen and oxygen using only heat or, in the case of a hybrid thermochemical process, by a combination of heat and electrolysis, could meet these goals. Hydrogen produced from

  8. Hydrogen generation from the hydrolysis of sodium borohydride using chemically modified multiwalled carbon nanotubes with pyridinium based ionic liquid and decorated with highly dispersed Mn nanoparticles

    Science.gov (United States)

    Chinnappan, Amutha; Puguan, John Marc C.; Chung, Wook-Jin; Kim, Hern

    2015-10-01

    Multiwalled carbon nanotubes (MWCNTs)/Ionic liquid (IL)/Mn nanohybrids are synthesized and their catalytic activity is examined for hydrogen generation from the hydrolysis of sodium borohydride (NaBH4). Transmission electron microscopy reveals that Mn nanoparticles well-distributed on the MWCNTs surface. Energy dispersive x-ray spectrometer and x-ray photoelectron spectroscopy confirms the presence of Mn and Ni atom in the nanohybrids. The nanohybrids exhibit excellent catalytic lifetime and gives the total turnover number of 18496 mol H2/mol catalyst in the hydrolysis of NaBH4, which can be attributed to the presence of Mn atom and IL containing nickel halide anion. It is worthy of note that a very small amount of catalyst is used for this hydrolysis reaction. The activation energy is found to be 40.8 kJ/mol by MWCNTs/IL/Mn nanohybrids from the kinetic study of the hydrogen generation from the hydrolysis of NaBH4. The improved hydrogen generation rate, lower activation energy, and less expensive make the nanohybrids promising candidate as catalyst for the hydrogen generation from NaBH4 solution. The nanohybrids are easy to prepare, store and yet catalytically active. The recycling process is very simple and further purification is not tedious.

  9. One-step preparation of biological aviation kerosene by catalytic hydrogenation of waste lard over Pt/SAPO-11

    Science.gov (United States)

    Zhang, X.; Chen, Y. B.; Li, X. Y.; Souliyathai, D.; Zhang, S. P.; Wang, Q.; Liu, Q.; Du, J. C.; Zhang, A. M.

    2017-11-01

    Biological aviation kerosene was produced by one-step catalytic hydrotreatment of waste lard oil over Pt/SAPO-11 in a high-pressure fixed bed micro reactor. The influence of reaction conditions such as temperature, pressure, hydrogen oil ratio, and space velocity on the deoxygenation rate, the selectivity of C8-C16 hydrocarbons and the isomerization rate of C8-C16 hydrocarbons have been investigated. The experimental results showed that the temperature of 400°C, pressure of 5 MPa, hydrogen oil ratio of 1000 and space velocity of 1.2 h-1 were the best experimental reaction conditions. Under these conditions, the conversion rate is 96.62%, the selectivity of C8-C16 hydrocarbons is 50.25%, and the isomerization rate of C8-C16 hydrocarbons is 35.68%.

  10. Session 4: Combinatorial research of methane catalytic decomposition on supported nitride catalysts for CO-free hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Jianghan, Shen; Hua, Wang; Zhongmin, Liu; Hongchao, Liu [Natural Gas Utilization and Applied Catalysis Lab., Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian P. R. (China)

    2004-07-01

    CO-free Hydrogen production is needed for proton exchange membrane fuel cells (PEMs) because CO strongly poisons the anode-electrocatalysts. Methane directly catalytic decomposition is an attractive way to produce CO-free hydrogen for the large abundance of methane and its high H/C ratio. It is more effective to employ high-throughput screening (HTS) technology in heterogeneous catalysis. In this paper, a combinatorial multi-stream reaction system with online multi-stream mass spectrometer screening (MSMSS) detection technique was applied to study the decomposition of methane over supported MoN{sub x}O{sub y} catalysts (supports = Al{sub 2}O{sub 3}, SiO{sub 2}, SBA-15, ZSM-5,13X, and NaY), which is a catalyst system seldom reported recently. (authors)

  11. Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media

    International Nuclear Information System (INIS)

    King, R.B.; Bhattacharyya, N.K.; Wiemers, K.D.

    1994-08-01

    Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 -, and NO 2 - were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO 2 H → H 2 + CO 2 catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100 degree C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl 3 ·3H 2 O, was found to be the most active catalyst for hydrogen generation from formic acid above ∼80 degree C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen production rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature (∼90 degree C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO 2 and NO/N 2 O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion

  12. Molecular metal-Oxo catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  13. One Step Hydrogen Generation Through Sorption Enhanced Reforming

    Energy Technology Data Exchange (ETDEWEB)

    Mays, Jeff [Gas Technology Inst., Des Plaines, IL (United States)

    2017-08-03

    One-step hydrogen generation, using Sorption Enhanced Reforming (SER) technology, is an innovative means of providing critical energy and environmental improvements to US manufacturing processes. The Gas Technology Institute (GTI) is developing a Compact Hydrogen Generator (CHG) process, based on SER technology, which successfully integrates previously independent process steps, achieves superior energy efficiency by lowering reaction temperatures, and provides pathways to doubling energy productivity with less environmental pollution. GTI’s prior CHG process development efforts have culminated in an operational pilot plant. During the initial pilot testing, GTI identified two operating risks- 1) catalyst coating with calcium aluminate compounds, 2) limited solids handling of the sorbent. Under this contract GTI evaluated alternative materials (one catalyst and two sorbents) to mitigate both risks. The alternate catalyst met performance targets and did not experience coating with calcium aluminate compounds of any kind. The alternate sorbent materials demonstrated viable operation, with one material enabling a three-fold increase in sorbent flow. The testing also demonstrated operation at 90% of its rated capacity. Lastly, a carbon dioxide co-production study was performed to assess the advantage of the solid phase separation of carbon dioxide- inherent in the CHG process. Approximately 70% lower capital cost is achievable compared to SMR-based hydrogen production with CO2 capture, as well as improved operating costs.

  14. Sum Frequency Generation Studies of Hydrogenation Reactions on Platinum Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Krier, James M. [Univ. of California, Berkeley, CA (United States)

    2013-08-31

    Sum Frequency Generation (SFG) vibrational spectroscopy is used to characterize intermediate species of hydrogenation reactions on the surface of platinum nanoparticle catalysts. In contrast to other spectroscopy techniques which operate in ultra-high vacuum or probe surface species after reaction, SFG collects information under normal conditions as the reaction is taking place. Several systems have been studied previously using SFG on single crystals, notably alkene hydrogenation on Pt(111). In this thesis, many aspects of SFG experiments on colloidal nanoparticles are explored for the first time. To address spectral interference by the capping agent (PVP), three procedures are proposed: UV cleaning, H2 induced disordering and calcination (core-shell nanoparticles). UV cleaning and calcination physically destroy organic capping while disordering reduces SFG signal through a reversible structural change by PVP.

  15. Catalytic Hydrogenation Activity and Electronic Structure Determination of Bis(arylimidazol-2-ylidene)pyridine Cobalt Alkyl and Hydride Complexes

    Science.gov (United States)

    Yu, Renyuan Pony; Darmon, Jonathan M.; Milsmann, Carsten; Margulieux, Grant W.; E. Stieber, S. Chantal; DeBeer, Serena

    2013-01-01

    The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, (iPrCNC)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 °C and 4 atm of H2 pressure, (iPrCNC)CoCH3 is an effective pre-catalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, (iPrCNC)CoH was accomplished by hydrogenation of (iPrCNC)CoCH3. Over the course of 3 hours at 22 °C, migration of the metal-hydride to the 4-position of the pyridine ring yielded (4-H2-iPrCNC)CoN2. Similar alkyl migration was observed upon treatment of (iPrCNC)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redoxactive, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity and suggest a wide family of pyridine-based pincers may also be redox active. PMID:23968297

  16. Pd/C Synthesized with Citric Acid: An Efficient Catalyst for Hydrogen Generation from Formic Acid/Sodium Formate

    Science.gov (United States)

    Wang, Zhi-Li; Yan, Jun-Min; Wang, Hong-Li; Ping, Yun; Jiang, Qing

    2012-01-01

    A highly efficient hydrogen generation from formic acid/sodium formate aqueous solution catalyzed by in situ synthesized Pd/C with citric acid has been successfully achieved at room temperature. Interestingly, the presence of citric acid during the formation and growth of the Pd nanoparticles on carbon can drastically enhance the catalytic property of the resulted Pd/C, on which the conversion and turnover frequency for decomposition of formic acid/sodium formate system can reach the highest values ever reported of 85% within 160 min and 64 mol H2 mol−1 catalyst h−1, respectively, at room temperature. The present simple, low cost, but highly efficient CO-free hydrogen generation system at room temperature is believed to greatly promote the practical application of formic acid system on fuel cells. PMID:22953041

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

    International Nuclear Information System (INIS)

    Azabou, Samia; Najjar, Wahiba; Bouaziz, Mohamed; Ghorbel, Abdelhamid; Sayadi, Sami

    2010-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Azabou, Samia [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia); Najjar, Wahiba [Laboratoire de Chimie des Materiaux et Catalyse, Faculte des Sciences de Tunis, Campus Universitaire, 2092 Tunis (Tunisia); Bouaziz, Mohamed [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia); Ghorbel, Abdelhamid [Laboratoire de Chimie des Materiaux et Catalyse, Faculte des Sciences de Tunis, Campus Universitaire, 2092 Tunis (Tunisia); Sayadi, Sami, E-mail: sami.sayadi@cbs.rnrt.tn [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia)

    2010-11-15

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

  19. Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen-Doped Carbon-Supported Iron Catalysts.

    Science.gov (United States)

    Li, Jiang; Liu, Jun-Ling; Zhou, Hong-Jun; Fu, Yao

    2016-06-08

    Iron-based heterogeneous catalysts, which were generally prepared by pyrolysis of iron complexes on supports at elevated temperature, were found to be capable of catalyzing the transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA). The effects of metal precursor, nitrogen precursor, pyrolysis temperature, and support on catalytic performance were examined thoroughly, and a comprehensive study of the reaction parameters was also performed. The highest selectivity of FFA reached 83.0 % with a FF conversion of 91.6 % under the optimal reaction condition. Catalyst characterization suggested that iron cations coordinated by pyridinic nitrogen functionalities were responsible for the enhanced catalytic activity. The iron catalyst could be recycled without significant loss of catalytic activity for five runs, and the destruction of the nitrogen-iron species, the presence of crystallized Fe2 O3 phase, and the pore structure change were the main reasons for catalyst deactivation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

    Science.gov (United States)

    Li, Yizhao; Cao, Yali; Jia, Dianzeng

    2018-01-01

    A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

  1. Optimized hydrogen generation in a semicontinuous sodium borohydride hydrolysis reactor for a 60 W-scale fuel cell stack

    Science.gov (United States)

    Arzac, G. M.; Fernández, A.; Justo, A.; Sarmiento, B.; Jiménez, M. A.; Jiménez, M. M.

    Catalyzed hydrolysis of sodium borohydride (SBH) is a promising method for the hydrogen supply of fuel cells. In this study a system for controlled production of hydrogen from aqueous sodium borohydride (SBH) solutions has been designed and built. This simple and low cost system operates under controlled addition of stabilized SBH solutions (fuel solutions) to a supported CoB catalyst. The system works at constant temperature delivering hydrogen at 1 L min -1 constant rate to match a 60-W polymer electrolyte membrane fuel cell (PEMFC). For optimization of the system, several experimental conditions were changed and their effect was investigated. A simple model based only on thermodynamic considerations was proposed to optimize system parameters at constant temperature and hydrogen evolution rate. It was found that, for a given SBH concentration, the use of the adequate fuel addition rate can maximize the total conversion and therefore the gravimetric storage capacity. The hydrogen storage capacity was as high as 3.5 wt% for 19 wt% SBH solution at 90% fuel conversion and an operation temperature of 60 °C. It has been demonstrated that these optimized values can also be achieved for a wide range of hydrogen generation rates. Studies on the durability of the catalyst showed that a regeneration step is needed to restore the catalytic activity before reusing.

  2. Conformational dynamics of free and catalytically active thermolysin are indistinguishable by hydrogen/deuterium exchange mass spectrometry.

    Science.gov (United States)

    Liu, Yu-Hong; Konermann, Lars

    2008-06-17

    Conformational dynamics are thought to be a prerequisite for the catalytic activity of enzymes. However, the exact relationship between structural fluctuations and function is not well understood. In this work hydrogen/deuterium exchange (HDX) and electrospray ionization mass spectrometry (ESI-MS) are used for exploring the conformational dynamics of thermolysin. Amide HDX reflects the internal mobility of proteins; regions that undergo frequent unfolding-refolding show faster exchange than segments that are highly stable. Thermolysin is a zinc protease with an active site that is located between two lobes. Substrate turnover is associated with hinge bending that leads to a closed conformation. Product release regenerates the open form, such that steady-state catalysis involves a continuous closing/opening cycle. HDX/ESI-MS with proteolytic peptide mapping in the absence of substrate shows that elements in the periphery of the two lobes are most mobile. A comparison with previous X-ray data suggests that these peripheral regions undergo quite pronounced structural changes during the catalytic cycle. In contrast, active site residues exhibit only a moderate degree of backbone flexibility, and the central zinc appears to be in a fairly rigid environment. The presence of both rigid and moderately flexible elements in the active site may reflect a carefully tuned balance that is required for function. Interestingly, the HDX behavior of catalytically active thermolysin is indistinguishable from that of the free enzyme. This result is consistent with the view that catalytically relevant motions preexist in the resting state and that enzyme function can only be performed within the limitations given by the intrinsic dynamics of the protein. The data presented in this work indicate the prevalence of stochastic elements in the function of thermolysin, rather than supporting a deterministic mechanism.

  3. Catalytic transfer hydrogenation/hydrogenolysis for reductive upgrading of furfural and 5-(hydroxymethyl)furfural.

    Science.gov (United States)

    Scholz, David; Aellig, Christof; Hermans, Ive

    2014-01-01

    The sequential transfer hydrogenation/hydrogenolysis of furfural and 5-hydroxymethylfurfural to 2-methylfuran and 2,5-dimethylfuran was studied over in situ reduced, Fe2 O3 -supported Cu, Ni, and Pd catalysts, with 2-propanol as hydrogen donor. The remarkable activity of Pd/Fe2 O3 in both transfer hydrogenation/hydrogenolysis is attributed to a strong metal-support interaction. Selectivity towards hydrogenation, hydrogenolysis, decarbonylation, and ring-hydrogenation products is shown to strongly depend on the Pd loading. A significant enhancement in yield to 62%, of 2-methylfuran and 2-methyltetrahydrofuran was observed under continuous flow conditions. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Reforming water to generate hydrogen using mechanical alloy

    International Nuclear Information System (INIS)

    Pena F, D. L.

    2016-01-01

    The objective of this research was to generate a hydrogen production system by means of mechanical milling, in which 0.1 g of magnesium were weighed using a volume of 300 μL for each water solvent (H 2 O) and methanol (CH 3 OH) in a container to start mechanical milling for 2, 4 and 6 h. Once the mechanical milling was finished, the hydrogen that was produced every two hours was measured to determine the appropriate milling time in the production, also in each period of time samples of the powders produced during the milling of Mg were taken, in this process we used characterization techniques such as: X-ray diffraction at an angle of 2θi 5 and 2θf 90 degrees and scanning electron microscopy, taking micrographs of 100, 500, 1000 and 5000 magnifications. According to the mechanical milling results hydrogen was obtained when using water, as well as with methanol. In the techniques of X-ray diffraction characterization different results were obtained before and after the milling, since by the diffractogram s is possible to observe how the magnesium to be put in the mechanical milling along with the water and methanol was diminishing to be transformed into hydroxide and magnesium oxide, as well as in the micrographs taken with scanning electron microscopy the change in the magnesium morphology to hydroxide and magnesium oxide is observed. (Author)

  5. Prediction of Improved Performance of Catalytic Hydrogenation Reactor by Periodic Modulation of the Feed Rate

    Czech Academy of Sciences Publication Activity Database

    Staněk, Vladimír; Hanika, Jiří; Jiřičný, Vladimír; Stavárek, Petr; Tukač, V.; Lederer, J.

    2009-01-01

    Roč. 23, č. 3 (2009), s. 251-257 ISSN 1451-9372 R&D Projects: GA MPO FT-TA/039 Institutional research plan: CEZ:AV0Z40720504 Keywords : trickle bed * feed modulation * catalytic reactor Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  6. Preparation of Rh/Ag bimetallic nanoparticles as effective catalyst for hydrogen generation from hydrolysis of KBH4

    Science.gov (United States)

    Huang, Liang; Jiao, Chengpeng; Wang, Liqiong; Huang, Zili; Liang, Feng; Liu, Simin; Wang, Yuhua; Zhang, Haijun; Zhang, Shaowei

    2018-01-01

    ISOBAM-104 protected Rh/Ag bimetallic nanoparticles (NPs) with average diameter less than 3.0 nm were synthesized by a co-reduction method. Ultraviolet–visible spectroscopy, transmission electron microscopy (TEM), high-resolution TEM and x-ray photoelectron spectroscopy (XPS) were employed to characterize the structure, particle size, and electronic structure of the prepared bimetallic NPs. The catalytic activities of prepared bimetallic NPs for hydrogen generation from hydrolysis of a basic KBH4 solution were evaluated in detail. The results indicated that as-prepared Rh/Ag bimetallic NPs showed a higher catalytic activity than corresponding monometallic NPs. Among all the monometallic NPs and bimetallic NPs, Rh80Ag20 bimetallic NPs exhibited the highest catalytic activity with a value of 6010 mol-H2·h‑1·mol-catalyst‑1 at pH = 12 and 303 K. The high catalytic activities of Rh/Ag bimetallic NPs could be attributed to presence of negatively charged Rh atoms and positively charged Ag atoms, which is supported by the results of XPS and density functional theory calculation. Based on the kinetic study, the apparent activation energy for the hydrolysis reaction of the basic KBH4 solution catalyzed by Rh80Ag20 bimetallic NPs was about 47.0 ± 3.9 kJ mol‑1.

  7. Life cycle assessment of hydrogenated biodiesel production from waste cooking oil using the catalytic cracking and hydrogenation method.

    OpenAIRE

    Yano, Junya; Aoki, Tatsuki; Nakamura, Kazuo; Yamada, Kazuo; Sakai, Shin-ichi

    2015-01-01

    There is a worldwide trend towards stricter control of diesel exhaust emissions, however presently, there are technical impediments to the use of FAME (fatty acid methyl esters)-type biodiesel fuel (BDF). Although hydrogenated biodiesel (HBD) is anticipated as a new diesel fuel, the environmental performance of HBD and its utilization system have not been adequately clarified. Especially when waste cooking oil is used as feedstock, not only biofuel production but also the treatment of waste c...

  8. Hydrazine as efficient fuel for low-temperature SOFC through ex-situ catalytic decomposition with high selectivity toward hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Song, Jia; Ran, Ran; Shao, Zongping [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, No. 5 Xin Mofan Road, Nanjing 210009 (China)

    2010-08-15

    Hydrazine is a promising fuel for portable fuel cells because it is a liquid, it is carbon free and it has a high energy density. In this work, hydrazine was investigated as an efficient fuel for low temperature solid-oxide fuel cells (SOFCs) with a traditional nickel anode. A catalytic system with high selectivity toward hydrogen was developed using Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} (BSCF) as the main catalyst and potassium hydroxide as the promoter. The result of compositional analysis of the products showed that the hydrazine can be decomposed into hydrogen and nitrogen with 100% selectivity when an appropriate amount of KOH promoter is used. Acceptable power densities were achieved for a thin-film samaria-doped ceria (SDC) electrolyte cell operating on hydrazine decomposition products and hydrogen over a complete operation temperature range of 650-450 C. In addition, a similar cell with ammonia as the fuel displayed a much lower performance. (author)

  9. System approach on solar hydrogen generation and the gas utilization; Taiyo energy ni yoru suiso no seisei oyobi sono riyo system ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, I.; Hirooka, N.; Deguchi, Y.; Narita, D. [Meiji University, Tokyo (Japan)

    1997-11-25

    An apparatus is developed to establish a system which allows utilization of hydrogen safely and easily, and its applicability to a hydrogen system for domestic purposes is tested. The system converts solar energy by the photovoltaic cell unit into power, which is used to generate hydrogen by electrolysis of water at the hydrogen generator, stores hydrogen in a metal hydride , and sends stored hydrogen to the burner and fuel cell units. It is found that a hydrogen occluding alloy of LaNi4.8Al0.2 stores hydrogen to approximately 80% when cooled to 20 to 25degC, and releases it to 10% when heated to 40degC. The fuel cell uses a solid polymer as the electrolyte. The hydrogen gas burner is a catalytic combustion burner with a Pt catalyst carried by expanded Ni-Al alloy. The optimum distance between the burner and object to be heated is 22mm. High safety and fabrication simplicity are confirmed for use for domestic purposes. The system characteristics will be further investigated. 4 refs., 8 figs.

  10. Enzyme catalytic resonance scattering spectral detection of trace hydrogen peroxide using guaiacol as substrate

    Directory of Open Access Journals (Sweden)

    Shiwen Huang

    2011-08-01

    Full Text Available Hydrogen peroxide oxidized guaiacol to form tetramer particles that exhibited a strong resonance scattering (RS peak at 530 nm in the presence of horseradish peroxidase (HRP in citric acid-Na2HPO4 buffer solution of pH 4.4. The RS peak increased when the concentration of hydrogen peroxide increased. The increased RS intensity (ΔI530 nm was linear to the hydrogen peroxide concentration in the range of 0.55-27.6 μM, with a linear regression equation of ΔI530 nm = 17.1C + 1.6, a relative coefficient of 0.9996 and a detection limit of 0.03 μM H2O2. This proposed method was applied to detect hydrogen peroxide in rain water, with sensitivity, selectivity, rapidity, and recovery of 98.0-104 %.

  11. Hybrid fiber gratings coated with a catalytic sensitive layer for hydrogen sensing in air.

    Science.gov (United States)

    Caucheteur, Christophe; Debliquy, Marc; Lahem, Driss; Megret, Patrice

    2008-10-13

    Using hydrogen as fuel presents a potential risk of explosion and requires low cost and efficient leak sensors. We present here a hybrid sensor configuration consisting of a long period fiber grating (LPFG) and a superimposed uniform fiber Bragg grating (FBG). Both gratings are covered with a sensitive layer made of WO(3) doped with Pt on which H(2) undergoes an exothermic reaction. The released heat increases the temperature around the gratings. In this configuration, the LPFG favors the exothermic reaction thanks to a light coupling to the sensitive layer while the FBG reflects the temperature change linked to the hydrogen concentration. Our sensor is very fast and suitable to detect low hydrogen concentrations in air whatever the relative humidity level and for temperatures down to -50 degrees C, which is without equivalent for other hydrogen optical sensors reported so far.

  12. Investigation of tritium removal by means of organic compounds. Catalytic hydrogenation (tritiation) of linoleic acid

    International Nuclear Information System (INIS)

    El-Sharnouby, A.; Weichselgartner, H.

    1984-11-01

    In the presence of noble-metal catalysts unsaturated fatty acids such as eruic acid and linoleic acid capture hydrogen (and tritium) quantitatively. The hydrogenation reaction of eruic acid has already been reported. The experimental results of the reaction of hydrogen (and tritium) with linoleic acid are now discussed in this paper. Obviously, the use of linoleic acid shows some advantages compared with eruic acid: - the hydrogenation reaction is faster, - linoleic acid is liquid, so that the choice of additional solvents is easier, and - linoleic acid is a more or less cheap natural product, which is available from a series of seeds, so that the cost of a technical tritium removal plant is not increased by the basic chemical material. (orig.)

  13. Maximizing renewable hydrogen production from biomass in a bio/catalytic refinery

    DEFF Research Database (Denmark)

    Westermann, Peter; Jørgensen, Betina; Lange, L.

    2007-01-01

    Biological production of hydrogen from biomass by fermentative or photofermentative microorganisms has been described in numerous research articles and reviews. The major challenge of these techniques is the low yield from fermentative production, and the large reactor volumes necessary...

  14. Catalytic activity of superconducting ceramics of Y-Ba-Cu-O type in reaction of H-D exchange of molecular hydrogen

    International Nuclear Information System (INIS)

    Parbuzin, V.S.; Gul'yants, V.V.

    1989-01-01

    Catalytic activity of high-temperature superconducting oxide ceramics of Y-Ba-Cu-O type in reaction of deuterium-hydrogen exchange was investigated under chromatographic conditions. Rate constants of the reaction and activation energy of the process, equal to 58 ± 2 kJ/mol, were determined in 350 - 450 K range and at 18250Pa hydrogen pressure. Assumption about applicability of Bonhoeffer-Farkas mechanism with adsorption on copper atoms, adjoinig oxygen vacancies, was made

  15. Thermal Balance Analysis of a Micro-Thermoelectric Gas Sensor Using Catalytic Combustion of Hydrogen

    Directory of Open Access Journals (Sweden)

    Daisuke Nagai

    2014-01-01

    Full Text Available A thermoelectric gas sensor (TGS with a combustion catalyst is a calorimetric sensor that changes the small heat of catalytic combustion into a signal voltage. We analyzed the thermal balance of a TGS to quantitatively estimate the sensor parameters. The voltage signal of a TGS was simulated, and the heat balance was calculated at two sections across the thermoelectric film of a TGS. The thermal resistances in the two sections were estimated from the thermal time constants of the experimental signal curves of the TGS. The catalytic combustion heat Qcatalyst required for 1 mV of ∆Vgas was calculated to be 46.1 μW. Using these parameters, we find from simulations for the device performance that the expected Qcatalyst for 200 and 1,000 ppm H2 was 3.69 μW and 11.7 μW, respectively.

  16. Thermal balance analysis of a micro-thermoelectric gas sensor using catalytic combustion of hydrogen.

    Science.gov (United States)

    Nagai, Daisuke; Akamatsu, Takafumi; Itoh, Toshio; Izu, Noriya; Shin, Woosuck

    2014-01-21

    A thermoelectric gas sensor (TGS) with a combustion catalyst is a calorimetric sensor that changes the small heat of catalytic combustion into a signal voltage. We analyzed the thermal balance of a TGS to quantitatively estimate the sensor parameters. The voltage signal of a TGS was simulated, and the heat balance was calculated at two sections across the thermoelectric film of a TGS. The thermal resistances in the two sections were estimated from the thermal time constants of the experimental signal curves of the TGS. The catalytic combustion heat Q(catalyst) required for 1 mV of ∆V(gas) was calculated to be 46.1 μW. Using these parameters, we find from simulations for the device performance that the expected Q(catalyst) for 200 and 1,000 ppm H₂ was 3.69 μW and 11.7 μW, respectively.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  18. Combining Ru, Ni and Ni(OH){sub 2} active sites for improving catalytic performance in benzene hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Lihua, E-mail: lihuazhu@stu.xmu.edu.cn [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Sun, Hanlei; Zheng, Jinbao [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Yu, Changlin, E-mail: yuchanglinjx@163.com [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zhang, Nuowei [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Shu, Qing [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Chen, Bing H., E-mail: chenbh@xmu.edu.cn [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2017-05-01

    In this study, the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were successfully prepared by the simple methods of hydrazine-reduction and galvanic replacement, where 0.04/0.96 and T represented the Ru/Ni atomic ratio and reducing temperature of the catalyst in N{sub 2}+10%H{sub 2}, respectively. The nanostructures of the Ru{sub 0.04}Ni{sub 0.96} nanoparticles in the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were controlled by modulating their annealing temperature in N{sub 2}+10%H{sub 2} and characterized by an array of techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy energy dispersive X-ray spectroscopy (STEM-EDS) mapping and high-sensitivity low-energy ion scattering (HS-LEIS). The Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, which was composed of Ru clusters or single atoms supported on Ni/Ni(OH){sub 2} nanoparticles, exhibited much better catalytic performance for benzene hydrogenation than the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts reduced at above 30 °C, such as Ru{sub 0.04}Ni{sub 0.96}/C(160) with the nanostructure of partial Ru{sub 0.04}Ni{sub 0.9} alloy and Ru{sub 0.04}Ni{sub 0.96}/C(280) with the nanostructure of complete Ru{sub 0.04}Ni{sub 0.9} alloy. The reason was that the synergistic effect of multiple active sites – Ru, Ni and Ni(OH){sub 2} sites was present in the Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, where hydrogen was preferentially activated at Ru sites, benzene was probably activated at Ni(OH){sub 2} surface and Ni acted as a “bridge” for transferring activated H{sup ∗} species to activated benzene by hydrogen spillover effect, hydrogenating and forming product – cyclohexane. This study also provided a typical example to illustrate that the synergy effect of multiple active sites can largely improve the catalytic hydrogenation performance. - Highlights: • The Ru

  19. High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

    Energy Technology Data Exchange (ETDEWEB)

    Bratlie, Kaitlin [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10-6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C6H11) and π-allyl C6H9, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C6H9, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C6H9 was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E2u mode of free benzene, which leads to catalysis. Linear C6 (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt

  20. Catalytic hydrogen production from fossil fuels via the water gas shift reaction

    International Nuclear Information System (INIS)

    Gradisher, Logan; Dutcher, Bryce; Fan, Maohong

    2015-01-01

    Highlights: • Hydrogen is a clean alternative to hydrocarbon fuels. • Hydrogen is primarily produced with the water gas shift reaction. • Development of water gas shift catalysts is essential to the energy industry. • This work summarizes recent progress in water gas shift catalyst research. - Abstract: The production of hydrogen is a highly researched topic for many reasons. First of all, it is a clean fuel that can be used instead of hydrocarbons, which produce CO 2 , a greenhouse gas emission that is thought to be the reason for climate change in the world. The largest source of hydrogen is the water gas shift (WGS) reaction, where CO and water are mixed over a catalyst to produce the desired hydrogen. Many researchers have focused on development of WGS catalysts with different metals. The most notable of these metals are precious and rare earth metals which, when combined, have unique properties for the WGS reaction. Research in this area is very important to the energy industry and the future of energy around the world. However, the progress made recently has not been reviewed, and this review was designed to fill the gap

  1. Synergic catalytic effect of Ti hydride and Nb nanoparticles for improving hydrogenation and dehydrogenation kinetics of Mg-based nanocomposite

    Directory of Open Access Journals (Sweden)

    Xiujuan Ma

    2017-02-01

    Full Text Available The Mg-9.3 wt% (TiH1.971-TiH−0.7 wt% Nb nanocomposite has been synthesized by hydrogen plasma-metal reaction (HPMR approach to enhance the hydrogen sorption kinetics of Mg at moderate temperatures by providing nanosizing effect of increasing H “diffusion channels” and adding transition metallic catalysts. The Mg nanoparticles (NPs were in hexagonal shape range from 50 to 350 nm and the average size of the NPs was 177 nm. The small spherical TiH1.971, TiH and Nb NPs of about 25 nm uniformly decorated on the surface of the big Mg NPs. The Mg-TiH1.971-TiH-Nb nanocomposite could quickly absorb 5.6 wt% H2 within 5 min at 573 K and 4.5 wt% H2 within 5 min at 523 K, whereas the pure Mg prepared by HPMR could only absorb 4 and 1.5 wt% H2 at the same temperatures. TiH1.971, TiH and Nb NPs transformed into TiH2 and NbH during hydrogenation and recovered after dehydrogenation process. The apparent activation energies of the nanocomposite for hydrogenation and dehydrogenation were 45.0 and 50.7 kJ mol−1, which are much smaller than those of pure Mg NPs, 123.8 and 127.7 kJ mol−1. The improved sorption kinetics of the Mg-based nanocomposite at moderate temperatures and the small activation energy can be interpreted by the nanostructure of Mg and the synergic catalytic effects of Ti hydrides and Nb NPs.

  2. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  3. HYDROGEN GENERATION FROM ELECTROLYSIS - REVISED FINAL TECHNICAL REPORT

    Energy Technology Data Exchange (ETDEWEB)

    IBRAHIM, SAMIR; STICHTER, MICHAEL

    2008-07-31

    DOE GO13028-0001 DESCRIPTION/ABSTRACT This report is a summary of the work performed by Teledyne Energy Systems to understand high pressure electrolysis mechanisms, investigate and address safety concerns related to high pressure electrolysis, develop methods to test components and systems of a high pressure electrolyzer, and produce design specifications for a low cost high pressure electrolysis system using lessons learned throughout the project. Included in this report are data on separator materials, electrode materials, structural cell design, and dissolved gas tests. Also included are the results of trade studies for active area, component design analysis, high pressure hydrogen/oxygen reactions, and control systems design. Several key pieces of a high pressure electrolysis system were investigated in this project and the results will be useful in further attempts at high pressure and/or low cost hydrogen generator projects. An important portion of the testing and research performed in this study are the safety issues that are present in a high pressure electrolyzer system and that they can not easily be simplified to a level where units can be manufactured at the cost goals specified, or operated by other than trained personnel in a well safeguarded environment. The two key objectives of the program were to develop a system to supply hydrogen at a rate of at least 10,000 scf/day at a pressure of 5000psi, and to meet cost goals of $600/ kW in production quantities of 10,000/year. On these two points TESI was not successful. The project was halted due to concerns over safety of high pressure gas electrolysis and the associated costs of a system which reduced the safety concerns.

  4. Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

    Science.gov (United States)

    Cao, Xinrui; Fu, Qiang; Luo, Yi

    2014-05-14

    The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

  5. An integrated MEMS infrastructure for fuel processing: hydrogen generation and separation for portable power generation

    Science.gov (United States)

    Varady, M. J.; McLeod, L.; Meacham, J. M.; Degertekin, F. L.; Fedorov, A. G.

    2007-09-01

    Portable fuel cells are an enabling technology for high efficiency and ultra-high density distributed power generation, which is essential for many terrestrial and aerospace applications. A key element of fuel cell power sources is the fuel processor, which should have the capability to efficiently reform liquid fuels and produce high purity hydrogen that is consumed by the fuel cells. To this end, we are reporting on the development of two novel MEMS hydrogen generators with improved functionality achieved through an innovative process organization and system integration approach that exploits the advantages of transport and catalysis on the micro/nano scale. One fuel processor design utilizes transient, reverse-flow operation of an autothermal MEMS microreactor with an intimately integrated, micromachined ultrasonic fuel atomizer and a Pd/Ag membrane for in situ hydrogen separation from the product stream. The other design features a simpler, more compact planar structure with the atomized fuel ejected directly onto the catalyst layer, which is coupled to an integrated hydrogen selective membrane.

  6. Modeling and Simulation of the Hydrogenation of α-Methylstyrene on Catalytically Active Metal Foams as Tubular Reactor Packing

    Directory of Open Access Journals (Sweden)

    Farzad Lali

    2016-01-01

    Full Text Available This work presents a one-dimensional reactor model for a tubular reactor packed with a catalytically active foam packing with a pore density of 30 PPI in cocurrent upward flow in the example of hydrogenation reaction of α-methylstyrene to cumene. This model includes material, enthalpy, and momentum balances as well as continuity equations. The model was solved within the parameter space applied for experimental studies under assumption of a bubbly flow. The method of orthogonal collocation on finite elements was applied. For isothermal and polytropic processes and steady state conditions, axial profiles for concentration, temperature, fluid velocities, pressure, and liquid holdup were computed and the conversions for various gas and liquid flow rates were validated with experimental results. The obtained results were also compared in terms of space time yield and catalytic activity with experimental results and stirred tank and also with random packed bed reactor. The comparison shows that the application of solid foams as reactor packing is advantageous compared to the monolithic honeycombs and random packed beds.

  7. High performing and stable supported nano-alloys for the catalytic hydrogenation of levulinic acid to γ-valerolactone

    Science.gov (United States)

    Luo, Wenhao; Sankar, Meenakshisundaram; Beale, Andrew M.; He, Qian; Kiely, Christopher J.; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

    2015-03-01

    The catalytic hydrogenation of levulinic acid, a key platform molecule in many biorefinery schemes, into γ-valerolactone is considered as one of the pivotal reactions to convert lignocellulose-based biomass into renewable fuels and chemicals. Here we report on the development of highly active, selective and stable supported metal catalysts for this reaction and on the beneficial effects of metal nano-alloying. Bimetallic random alloys of gold-palladium and ruthenium-palladium supported on titanium dioxide are prepared with a modified metal impregnation method. Gold-palladium/titanium dioxide shows a marked,~27-fold increase in activity (that is, turnover frequency of 0.1 s-1) compared with its monometallic counterparts. Although ruthenium-palladium/titanium dioxide is not only exceptionally active (that is, turnover frequency of 0.6 s-1), it shows excellent, sustained selectivity to γ-valerolactone (99%). The dilution and isolation of ruthenium by palladium is thought to be responsible for this superior catalytic performance. Alloying, furthermore, greatly improves the stability of both supported nano-alloy catalysts.

  8. Solar photo-catalytic hydrogen: systems considerations, economics, and potential markets. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Steele, R V; Witwer, J G

    1981-05-01

    A three part analysis was done consisting of (1) an examination of the physical principles of solar photocatalytic energy conversion and the status of research in this area, (2) an economic analysis of the potential costs of producing hydrogen from such a system, and (3) an analysis of the markets for hydrogen and the possible penetration of these markets by solar photocatalytic hydrogen. The cost range of flat plate thermal collectors, heliostats, and a photovoltaic system are compared. The cost range of flat plate thermal collectors was used to represent the cost of photocatalytic systems. On the basis of the photovoltaics cost outlook, it is found that photocatalytic systems would not cost less than $180 to $330 per m/sup 2/ range. On the basis of the heliostat cost outlook, a cost lower than $180 to $330 per m could be projected only for very large production volumes and very large installations. (LEW)

  9. Hydrogen and Carbon Nanotubes Production by Catalytic of Ethanol Over the Co-Mo Catalysts.

    Science.gov (United States)

    Diao, Jinxiang; Wang, Gang; Liu, Xiaojie; Wang, Hui

    2018-06-01

    A series of Cobalt-Carbon, Cobalt-Molybdenum-Carbon catalysts were prepared by impregnation. The molar ratios of Co:Mo were 9:1, 8:2 and 7:3 and the total metal weights of them in the supported catalysts were 5 wt%. Moreover, the effects of reaction temperature and the Co:Mo molar ratios on the produce hydrogen and carbon nanotubes were investigated systematically. Of all the catalysts, Co-Mo (5 wt%, Co:Mo = 9:1)/C was the most effective one on the basis of hydrogen yield (84%), ethanol conversion (95%) and the quality of carbon nanotubes at 600 °C. A small amount of Mo added into the Co/C catalysts resulted in increasing in the yield of hydrogen and improving on quality of carbon nanotubes from ethanol decomposition over the Co-Mo catalysts.

  10. Catalytic reduction of nitrate and nitrite ions by hydrogen : investigation of the reaction mechanism over Pd and Pd-Cu catalysts

    NARCIS (Netherlands)

    Ilinitch, OM; Nosova, LV; Gorodetskii, VV; Ivanov, VP; Trukhan, SN; Gribov, EN; Bogdanov, SV; Cuperus, FP

    2000-01-01

    The catalytic behavior of mono- and bimetallic catalysts with Pd and/or Cu supported over gamma-Al2O3 in the reduction of aqueous nitrate and nitrite ions by hydrogen was investigated. The composition of the supported metal catalysts was analysed using secondary ion mass spectroscopy (SIMS) and

  11. Negative Effect of Calcination to Catalytic Performance of Coal Char-loaded TiO2 Catalyst in Styrene Oxidation with Hydrogen Peroxide as Oxidant

    Directory of Open Access Journals (Sweden)

    Mukhamad Nurhadi

    2018-01-01

    How to Cite: Nurhadi, M., Kusumawardani, R., Nur, H. (2018. Negative Effect of Calcination to Catalytic Performance of Coal Char-loaded TiO2 Catalyst in Styrene Oxidation with Hydrogen Peroxide as Oxidant. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 113-118 (doi:10.9767/bcrec.13.1.1171.113-118

  12. Surface- and interface-engineered heterostructures for solar hydrogen generation

    Science.gov (United States)

    Chen, Xiangyan; Li, Yanrui; Shen, Shaohua

    2018-04-01

    Photoelectrochemical (PEC) water splitting based on semiconductor photoelectrodes provides a promising platform for reducing environmental pollution and solving the energy crisis by developing clean, sustainable and environmentally friendly hydrogen energy. In this context, metal oxides with their advantages including low cost, good chemical stability and environmental friendliness, have attracted extensive attention among the investigated candidates. However, the large bandgap, poor charge transfer ability and high charge recombination rate limit the PEC performance of metal oxides as photoelectrodes. To solve this limitation, many approaches toward enhanced PEC water splitting performance, which focus on surface and interface engineering, have been presented. In this topical review, we concentrate on the heterostructure design of some typical metal oxides with narrow bandgaps (e.g. Fe2O3, WO3, BiVO4 and Cu2O) as photoelectrodes. An overview of the surface- and interface-engineered heterostructures, including semiconductor heterojunctions, surface protection, surface passivation and cocatalyst decoration, will be given to introduce the recent advances in metal oxide heterostructures for PEC water splitting. This article aims to provide fundamental references and principles for designing metal oxide heterostructures with high activity and stability as photoelectrodes for PEC solar hydrogen generation.

  13. Generation of hydrogen free radicals from water for fuels by electric field induction

    International Nuclear Information System (INIS)

    Nong, Guangzai; Chen, Yiyi; Li, Ming; Zhou, Zongwen

    2015-01-01

    Highlights: • Hydrogen free radicals are generated from water splitting. • Hydrogen fuel is generated from water by electric field induction. • Hydrocarbon fuel is generated from CO 2 and water by electric field induction. - Abstract: Water is the most abundant resource for generating hydrogen fuel. In addition to dissociating H + and − OH ions, certain water molecules dissociate to radicals under an electric field are considered. Therefore, an electric field inducing reactor is constructed and operated to generate hydrogen free radicals in this paper. Hydrogen free radicals begin to be generated under a 1.0 V electric field, and increasing the voltage and temperature increases the number of hydrogen free radicals. The production rate of hydrogen free radicals is 0.245 mmol/(L h) at 5.0 V and room temperature. The generated hydrogen free radicals are converted to polymer fuel and hydrogen fuel at production rates of 0.0093 mmol/(L h) and 0.0038 mmol/(L h) respectively, under 5.0 V and 0.25 mA. The results provide a way to generate hydrogen free radicals, which might be used to generate hydrocarbon fuel in industrial manufacture.

  14. Combustion of hydrogen-oxygen mixture in electrochemically generated nanobubbles.

    Science.gov (United States)

    Svetovoy, Vitaly B; Sanders, Remko G P; Lammerink, Theo S J; Elwenspoek, Miko C

    2011-09-01

    Ignition of exothermic chemical reactions in small volumes is considered as difficult or impossible due to the large surface-to-volume ratio. Here observation of the spontaneous reaction is reported between hydrogen and oxygen in bubbles whose diameter is smaller than a threshold value around 150 nm. The effect is attributed to high Laplace pressure and to fast dynamics in nanobubbles and is the first indication on combustion in the nanoscale. In this study the bubbles were produced by water electrolysis using successive generation of H(2) and O(2) above the same electrode with short voltage pulses in the microsecond range. The process was observed in a microsystem at current densities >1000 A/cm(2) and relative supersaturations >1000.

  15. Next-generation TCAP hydrogen isotope separation process

    International Nuclear Information System (INIS)

    Heung, L. K.; Sessions, H. T.; Poore, A. S.; Jacobs, W. D.; Williams, C. S.

    2008-01-01

    A thermal cycling absorption process (TCAP) for hydrogen isotope separation has been in operation at Savannah River Site since 1994. The process uses a hot/cold nitrogen system to cycle the temperature of the separation column. The hot/cold nitrogen system requires the use of large compressors, heat exchanges, valves and piping that is bulky and maintenance intensive. A new compact thermal cycling (CTC) design has recently been developed. This new design uses liquid nitrogen tubes and electric heaters to heat and cool the column directly so that the bulky hot/cold nitrogen system can be eliminated. This CTC design is simple and is easy to implement, and will be the next generation TCAP system at SRS. A twelve-meter column has been fabricated and installed in the laboratory to demonstrate its performance. The design of the system and its test results to date is discussed. (authors)

  16. Broad Spectrum Photoelectrochemical Diodes for Solar Hydrogen Generation

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Craig A.

    2014-11-26

    Under program auspices we have investigated material chemistries suitable for the solar generation of hydrogen by water photoelectrolysis. We have built upon, and extended, our knowledge base on the synthesis and application of TiO2 nanotube arrays, a material architecture that appears ideal for water photoelectrolysis. To date we have optimized, refined, and greatly extended synthesis techniques suitable for achieving highly ordered TiO2 nanotube arrays of given length, wall thickness, pore diameter, and tube-to-tube spacing for use in water photoelectrolysis. We have built upon this knowledge based to achieve visible light responsive, photocorrosion stable n-type and p-type ternary oxide nanotube arrays for use in photoelectrochemical diodes.

  17. Sustainable hydrogen from bio-oil - Catalytic steam reforming of acetic acid as a model oxygenate

    NARCIS (Netherlands)

    Takanabe, Kazuhiro; Seshan, K.; Lefferts, Leon; Aika, Ken-ichi

    2004-01-01

    Steam reforming of acetic acid as a model oxygenate present in bio-oil over Pt/ZrO2 catalysts has been studied. Pt/ZrO2 catalysts are very active, completely converting acetic acid and give hydrogen yield close to thermodynamic equilibrium. The catalyst deactivated by formation of oligomers, which

  18. Continuous-flow catalytic asymmetric hydrogenations: Reaction optimization using FTIR inline analysis

    Directory of Open Access Journals (Sweden)

    Magnus Rueping

    2012-02-01

    Full Text Available The asymmetric organocatalytic hydrogenation of benzoxazines, quinolines, quinoxalines and 3H-indoles in continuous-flow microreactors has been developed. Reaction monitoring was achieved by using an inline ReactIR flow cell, which allows fast and convenient optimization of reaction parameters. The reductions proceeded well, and the desired products were isolated in high yields and with excellent enantioselectivities.

  19. Catalytic Ring Hydrogenation of Benzoic Acid with Supported Transition Metal Catalysts in scCO2

    Directory of Open Access Journals (Sweden)

    Fengyu Zhao

    2007-07-01

    Full Text Available The ring hydrogenation of benzoic acid to cyclohexanecarboxylic acid overcharcoal-supported transition metal catalysts in supercritical CO2 medium has been studiedin the present work. The cyclohexanecarboxylic acid can be produced efficiently insupercritical CO2 at the low reaction temperature of 323 K. The presence of CO2 increasesthe reaction rate and several parameters have been discussed.

  20. In situ diffraction study of catalytic hydrogenation of VO₂: stable phases and origins of metallicity.

    Science.gov (United States)

    Filinchuk, Yaroslav; Tumanov, Nikolay A; Ban, Voraksmy; Ji, Heng; Wei, Jiang; Swift, Michael W; Nevidomskyy, Andriy H; Natelson, Douglas

    2014-06-04

    Controlling electronic population through chemical doping is one way to tip the balance between competing phases in materials with strong electronic correlations. Vanadium dioxide exhibits a first-order phase transition at around 338 K between a high-temperature, tetragonal, metallic state (T) and a low-temperature, monoclinic, insulating state (M1), driven by electron-electron and electron-lattice interactions. Intercalation of VO2 with atomic hydrogen has been demonstrated, with evidence that this doping suppresses the transition. However, the detailed effects of intercalated H on the crystal and electronic structure of the resulting hydride have not been previously reported. Here we present synchrotron and neutron diffraction studies of this material system, mapping out the structural phase diagram as a function of temperature and hydrogen content. In addition to the original T and M1 phases, we find two orthorhombic phases, O1 and O2, which are stabilized at higher hydrogen content. We present density functional calculations that confirm the metallicity of these states and discuss the physical basis by which hydrogen stabilizes conducting phases, in the context of the metal-insulator transition.

  1. H2CAP – Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Stummann, Magnus Zingler; Høj, Martin; Gabrielsen, Jostein

    . The objective of thepresent work is to convert biomass into gasoline and diesel. Fast pyrolysis of beech wood have beenconducted at high hydrogen pressure in a fluid bed reactor with a hydrodeoxygenation (HDO) catalyst asbed medium followed by a fixed bed HDO reactor for complete oxygen removal before oil...

  2. Catalytic hydrogenation of polyaromatic hydrocarbon (PAH) compounds in supercritical carbon dioxide over supported palladium.

    Science.gov (United States)

    Yuan, Tao; Marshall, William D

    2007-12-01

    A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen-carbon dioxide [5% (w/w) H(2)/CO(2)] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 degrees C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography-mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or gamma-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on gamma-alumina were more efficient than a commercial Pd(0) (5% w/w) on gamma-Al(2)O(3) formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO(2)) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe(0) formulations.

  3. Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu; Aliaga, Cesar; Hung, Ling-I; Somorjai, Gabor A.; Yang, Peidong

    2009-03-02

    Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H2 chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.

  4. Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins

    Science.gov (United States)

    Xiang, Yizhi; Kruse, Norbert

    2016-10-01

    The catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. While traditionally mainly methanol and long-chain hydrocarbons are produced by CO hydrogenation, here we show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts. The sum selectivity of aldehydes and alcohols is usually >50 wt% whereof up to ~97% can be n-aldehydes. While the product slate contains ~60% n-aldehydes at /pCO=0.5, a 65/35% slate of paraffins/alcohols is obtained at a ratio of 9. A linear Anderson-Schulz-Flory behaviour, independent of the /pCO ratio, is found for the sum of C4+ products. We advocate a synergistic interaction between a Mn5O8 oxide and a bulk Co2C phase, promoted by the presence of potassium, to be responsible for the unique product spectra in our studies.

  5. Interdisciplinary study of the influence on effectiveness of catalytic hydrogen recombiners of operating conditions in the reactor containment

    International Nuclear Information System (INIS)

    Kelm, S.; Reinecke, E.A.; Schoppe, L.; Dornseiffer, J.; Leistner, F.; Juehe, S.

    2008-01-01

    At the Emsland nuclear power station, a total of 58 autocatalytic hydrogen recombiners were backfitted in 1999 as an additional measure of risk reduction in connection with major hydrogen releases after events going beyond the design basis. Annual in-service inspections after 2002 revealed that some of the catalyst sheets developed startup delays and marked evolutions of smoke and smell. Recombiners not meeting the inspection criterion were completely regenerated as a measure of precaution. A preventive study was conducted jointly with institutes of the Juelich Research Center and the Aachen Technical University to analyze the composition of the deposits, which was then compared with the chemical characteristics of potential sources in the reactor containment. At the same time, the influence on effectiveness of the catalyst sheets was examined. On the basis of a random evaluation of the in-service inspection logs of the past few years, representative samples were taken whose startup behavior and operating characteristics were studied in a test rig alongside chemical analyses so as to allow a correlation to be established between the analytical findings and the catalytic activity of the samples. The findings made allowed internal sources of the catalyst deposits to be excluded. The impurities are introduced with the outside air. As a consequence, the air ducts in the vicinity of the respective recombiners were inspected and optimization steps were taken in connection with in-service inspections and regeneration procedures. (orig.)

  6. Experimental studies on catalytic hydrogen recombiners for light water reactors; Experimentelle Untersuchungen zu katalytischen Wasserstoffkombinatoren fuer Leichtwasserreaktoren

    Energy Technology Data Exchange (ETDEWEB)

    Drinovac, P.

    2006-06-19

    In the course of core melt accidents in nuclear power plants a large amount of hydrogen can be produced and form an explosive or even detonative gas mixture with aerial oxygen in the reactor building. In the containment atmosphere of pressurized water reactors hydrogen combines a phlogistically with the oxygen present to form water vapor even at room temperature. In the past, experimental work conducted at various facilities has contributed little or nothing to an understanding of the operating principles of catalytic recombiners. Hence, the purpose of the present study was to conduct detailed investigations on a section of a recombiner essentially in order to deepen the understanding of reaction kinetics and heat transport processes. The results of the experiments presented in this dissertation form a large data base of measurements which provides an insight into the processes taking place in recombiners. The reaction-kinetic interpretation of the measured data confirms and deepens the diffusion theory - proposed in an earlier study. Thus it is now possible to validate detailed numeric models representing the processes in recombiners. Consequently the present study serves to broaden and corroborate competence in this significant area of reactor technology. In addition, the empirical knowledge thus gained may be used for a critical reassessment of previous numeric model calculations. (orig.)

  7. Systems and methods for generation of hydrogen peroxide vapor

    Science.gov (United States)

    Love, Adam H; Eckels, Joel Del; Vu, Alexander K; Alcaraz, Armando; Reynolds, John G

    2014-12-02

    A system according to one embodiment includes a moisture trap for drying air; at least one of a first container and a second container; and a mechanism for at least one of: bubbling dried air from the moisture trap through a hydrogen peroxide solution in the first container for producing a hydrogen peroxide vapor, and passing dried air from the moisture trap into a headspace above a hydrogen peroxide solution in the second container for producing a hydrogen peroxide vapor. A method according one embodiment includes at least one of bubbling dried air through a hydrogen peroxide solution in a container for producing a first hydrogen peroxide vapor, and passing dried air from the moisture trap into a headspace above the hydrogen peroxide solution in a container for producing a second hydrogen peroxide vapor. Additional systems and methods are also presented.

  8. A study of the effect of gamma radiation and doping on the catalytic activity of some oxides in the decomposition of hydrogen per-oxide

    International Nuclear Information System (INIS)

    Mousa, M.A.

    1987-01-01

    The rates of hydrogen peroxide decomposition on pure, doped and gamma-irradiated oxides Chromium oxide, Cobalt oxide, Magnesium oxide Nickel oxide, Ferric oxide, Magnesium ferri oxide were measured in a temperature range of 25-40 degree centigrade. It was found that lattice defect induced by doping and gamma-irradiation affect the catalytic properties of the oxides, either by activation or deactivation. The correlation between the catalytic activity for the hydrogen peroxide decomposition and the electronic defects produced by doping and by gamma-irradiation in the oxides is dicussed. Generally, it was found that the p-type semiconductor oxides are more active towards hydrogen peroxide decomposition than the n-type semiconductor oxides. (orig./A.B.)

  9. Spark Discharge Generated Nanoparticles for Hydrogen Storage Applications

    NARCIS (Netherlands)

    Vons, V.A.

    2010-01-01

    One of the largest obstacles to the large scale application of hydrogen powered fuel cell vehicles is the absence of hydrogen storage methods suitable for application on-board of these vehicles. Metal hydrides are materials in which hydrogen is reversibly absorbed by one or more metals or

  10. An Improved Strategy for the Synthesis of Ethylene Glycol by Oxamate-Mediated Catalytic Hydrogenation.

    Science.gov (United States)

    Satapathy, Anilkumar; Gadge, Sandip T; Bhanage, Bhalchandra M

    2017-04-10

    The present study reports an improved approach for the preparation of ethylene glycol (EG) by using carbon monoxide as C1 chemical by a two-step oxidative carbonylation and hydrogenation sequence. In the first step, oxamates are synthesized through oxidative cross double carbonylation of piperidine and ethanol by using Pd/C catalyst under phosphine ligand-free conditions and subsequently hydrogenated by Milstein's catalyst (carbonylhydrido[6-(di-t-butylphosphinomethylene)-2-(N,N-diethylaminomethyl)-1,6-dihydropyridine]ruthenium(II)). The presented stepwise oxamate-mediated coupling provides the basis for a new strategy for the synthesis of EG by selective upgrading of C1 chemicals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The reduction of carbon dioxide in iron biocatalyst catalytic hydrogenation reaction: a theoretical study.

    Science.gov (United States)

    Yang, Longhua; Wang, Hongming; Zhang, Ning; Hong, Sanguo

    2013-08-21

    The reaction mechanism of CO₂ hydrogenation catalyzed by [FeH(PP₃)]BF₄ (PP₃ = P(CH₂CH₂PPh₂)₃) had been investigated by DFT calculations. Our calculations indicated that the reduction of carbon dioxide could be carried out via two spin states, the high-spin (HS) triplet state and the low-spin (LS) singlet state. The minimum energy crossing points (MECPs) on the seam of two intersecting PESs (potential energy surfaces) were searched out. Some interesting phenomena, such as the open-loop phenomenon, and the O-rebound process, were demonstrated to be the important causes of the spin crossover. All these calculations gave us insight into the essence of the related experiment from the macro point of view, and helped to verify which spin states the related complexes pertinent were in. All of these researches would help advance the development of efficient and structurally tailorable CO₂ hydrogenation catalysts.

  12. Study on the synthesis of dimethyl 1,4-cyclohexanedicarboxylate by catalytic hydrogenation of dimethyl terephthalate

    Directory of Open Access Journals (Sweden)

    LI Yuanhua

    2016-12-01

    Full Text Available In the field of polymer industry,1,4-cyclohexanedimethanol (CHDM occupies an important position especially for the synthesis of highly valued polyester products.In industry,CHDM is prepared from dimethyl terephthalate (DMT through a two-step hydrogenation process Palladium supported on magnesium oxide (Pd/MgO was prepared by animpregnation method and was characterized by x-ray diffraction (XRD,transmission electron microscope (TEM and scan electron microscope (SEM.During the hydrogenation of DMT to synthesize dimethyl 1,4-cyclohexanedicarboxylate (DMCD,the as-prepared Pd/MgO was used as the catalyst with methyl acetate as the solvent.Under optimized reaction conditions (reaction temperature:180 ℃,reaction pressure:4.5 MPa,the conversion of DMT was 100% and the selectivity of DMCD was 99%.Such a catalyst shows a good potential in industrial applications.

  13. Numerical study of methanol–steam reforming and methanol–air catalytic combustion in annulus reactors for hydrogen production

    International Nuclear Information System (INIS)

    Chein, Reiyu; Chen, Yen-Cho; Chung, J.N.

    2013-01-01

    Highlights: ► Performance of mini-scale integrated annulus reactors for hydrogen production. ► Flow rates fed to combustor and reformer control the reactor performance. ► Optimum performance is found from balance of flow rates to combustor and reformer. ► Better performance can be found when shell side is designed as combustor. -- Abstract: This study presents the numerical simulation on the performance of mini-scale reactors for hydrogen production coupled with liquid methanol/water vaporizer, methanol/steam reformer, and methanol/air catalytic combustor. These reactors are designed similar to tube-and-shell heat exchangers. The combustor for heat supply is arranged as the tube or shell side. Based on the obtained results, the methanol/air flow rate through the combustor (in terms of gas hourly space velocity of combustor, GHSV-C) and the methanol/water feed rate to the reformer (in terms of gas hourly space velocity of reformer, GHSV-R) control the reactor performance. With higher GHSV-C and lower GHSV-R, higher methanol conversion can be achieved because of higher reaction temperature. However, hydrogen yield is reduced and the carbon monoxide concentration is increased due to the reversed water gas shift reaction. Optimum reactor performance is found using the balance between GHSV-C and GHSV-R. Because of more effective heat transfer characteristics in the vaporizer, it is found that the reactor with combustor arranged as the shell side has better performance compared with the reactor design having the combustor as the tube side under the same operating conditions.

  14. COx Free Hydrogen Production by Catalytic Decomposition of Methane Over Porous Ni/Al2O3 Catalysts

    International Nuclear Information System (INIS)

    Makvandi, S.; Alavi, S. M.

    2011-01-01

    The prepared meso porous spherical alumina with high-surface area was employed as a support for nickel catalysts in methane decomposition reaction. It was observed that, the catalytic activity of Ni/Al 2 O 3 catalysts was high at the initial times of reaction and decreased with time on stream, and finally reached a constant value. The deactivation rate of catalysts is dependent on the catalyst characteristics and the operating conditions. The activity results indicate that, the yield of hydrogen and the structure of deposited carbon are strongly dependent on the loading amount of Ni. The Scanning Electron Microscopy results showed that carbon formed on the catalysts in the form of filamentous carbon. Concerning hydrogen production, the 10% Ni/ Al 2 O 3 catalyst leads to a higher yield, due to the higher amount of active phases which can catalyze further the number of methane molecules, while lesser amounts of filamentous carbon were observed on this catalyst than for 5 and 7.5% Ni/ Al 2 O 3 catalysts at the same operating condition. The yield of hydrogen and structure of filamentous carbon also significantly depend on the reaction temperatures and residence time of gas in the reactor, as the 10% Ni/ Al 2 O 3 catalyst showed a remarkable stability with a decrease of about 14% at 800 d egree C and 25 ml/min after 240 min of reaction. The obtained results showed that the prepared Ni/ Al 2 O 3 catalysts had a good activity in methane decomposition reaction, which is one of the highest activities among those for low nickel loaded catalysts reported up until now.

  15. Interfacial electrochemistry of colloidal ruthenium dioxide and catalysis of the photochemical generation of hydrogen from water

    NARCIS (Netherlands)

    Kleijn, J.M.

    1987-01-01

    The formation of hydrogen from water using solar energy is a very attractive research topic, because of the potential use of hydrogen as an alternative, clean fuel. It has been shown by many workers in the field that photochemical hydrogen generation can be achieved in an aqueous system,

  16. Influence of Adsorption Geometry in the Heterogeneous Enantioselective Catalytic Hydrogenation of a Prototypical Enone

    OpenAIRE

    Beaumont, SK; Kyriakou, G; Watson, DJ; Vaughan, OPH; Papageorgiou, AC; Lambert, RM

    2010-01-01

    Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanopart...

  17. Low-Energy Catalytic Electrolysis for Simultaneous Hydrogen Evolution and Lignin Depolymerization.

    Science.gov (United States)

    Du, Xu; Liu, Wei; Zhang, Zhe; Mulyadi, Arie; Brittain, Alex; Gong, Jian; Deng, Yulin

    2017-03-09

    Here, a new proton-exchange-membrane electrolysis is presented, in which lignin was used as the hydrogen source at the anode for hydrogen production. Either polyoxometalate (POM) or FeCl 3 was used as the catalyst and charge-transfer agent at the anode. Over 90 % Faraday efficiency was achieved. In a thermal-insulation reactor, the heat energy could be maintained at a very low level for continuous operation. Compared to the best alkaline-water electrolysis reported in literature, the electrical-energy consumption could be 40 % lower with lignin electrolysis. At the anode, the Kraft lignin (KL) was oxidized to aromatic chemicals by POM or FeCl 3 , and reduced POM or Fe ions were regenerated during the electrolysis. Structure analysis of the residual KL indicated a reduction of the amount of hydroxyl groups and the cleavage of ether bonds. The results suggest that POM- or FeCl 3 -mediated electrolysis can significantly reduce the electrolysis energy consumption in hydrogen production and, simultaneously, depolymerize lignin to low-molecular-weight value-added aromatic chemicals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Kelm, S.; Reinecke, E-A.; Jahn, W.; Allelein, H-J.

    2011-01-01

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

  19. Catalytic performance and characterization of cobalt-nickel nano catalysts for CO hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Feyzi, Mostafa; Gholivand, Mohammad Bagher [Razi University, Kermanshah (Iran, Islamic Republic of); Babakhanian, Arash [Islamic Azad University, Kermanshah (Iran, Islamic Republic of)

    2014-01-15

    A series of Co-Ni nano catalysts were prepared by co-precipitation method. We investigated the effect of Co/Ni molar ratios precipitate and calcination conditions on the catalytic performance of cobalt nickel catalysts for Fisher-Tropsch synthesis (FTS). The catalyst containing 90%Co/10%Ni was found to be optimal for the conversion of synthesis gas to light olefins. The activity and selectivity of the optimal catalyst were studied in different operational conditions. The results show that the best operational conditions are the H{sub 2}/CO=2/1 molar feed ratio at 310 .deg. C and GHSV=1,200 h{sup -}1 under 5 bar of pressure. The prepared catalysts were characterized by powder X-ray diffraction (XRD), N{sub 2} adsorption-desorption measurements such as BET and BJH methods, transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA)

  20. Biomedical and Forensic Applications of Combined Catalytic Hydrogenation-Stable Isotope Ratio Analysis

    Science.gov (United States)

    Sephton, Mark A.; Meredith, Will; Sun, Cheng-Gong; Snape, Colin E.

    2007-01-01

    Studies of biological molecules such as fatty acids and the steroid hormones have the potential to benefit enormously from stable carbon isotope ratio measurements of individual molecules. In their natural form, however, the body’s molecules interact too readily with laboratory equipment designed to separate them for accurate measurements to be made. Some methods overcome this problem by adding carbon to the target molecule, but this can irreversibly overprint the carbon source ‘signal’. Hydropyrolysis is a newly-applied catalytic technique that delicately strips molecules of their functional groups but retains their carbon skeletons and stereochemistries intact, allowing precise determination of the carbon source. By solving analytical problems, the new technique is increasing the ability of scientists to pinpoint molecular indicators of disease, elucidate metabolic pathways and recognise administered substances in forensic investigations. PMID:19662175

  1. Biomedical and Forensic Applications of Combined Catalytic Hydrogenation-Stable Isotope Ratio Analysis

    Directory of Open Access Journals (Sweden)

    Mark A. Sephton

    2007-01-01

    Full Text Available Studies of biological molecules such as fatty acids and the steroid hormones have the potential to benefit enormously from stable carbon isotope ratio measurements of individual molecules. In their natural form, however, the body’s molecules interact too readily with laboratory equipment designed to separate them for accurate measurements to be made.Some methods overcome this problem by adding carbon to the target molecule, but this can irreversibly overprint the carbon source ‘signal’. Hydropyrolysis is a newly-applied catalytic technique that delicately strips molecules of their functional groups but retains their carbon skeletons and stereochemistries intact, allowing precise determination of the carbon source. By solving analytical problems, the new technique is increasing the ability of scientists to pinpoint molecular indicators of disease, elucidate metabolic pathways and recognise administered substances in forensic investigations.

  2. Computational design of materials for solar hydrogen generation

    Science.gov (United States)

    Umezawa, Naoto

    Photocatalysis has a great potential for the production of hydrogen from aquerous solution under solar light. In this talk, two different approaches toward the computational materials desing for solar hydrogen generation will be presented. Tin (Sn), which has two major oxidation states, Sn2+ and Sn4+, is abundant on the earth's crust. Recently, visible-light responsive photocatalytc H2 evolution reaction was identified over a mixed valence tin oxide Sn3O4. We have carried out crystal structure prediction for mixed valence tin oxides in different atomic compositions under ambient pressure condition using advanced computational methods based on the evolutionary crystal-structure search and density-functional theory. The predicted novel crystal structures realize the desirable band gaps and band edge positions for H2 evolution under visible light irradiation. It is concluded that multivalent tin oxides have a great potential as an abundant, cheap and environmentally-benign solar-energy conversion photofunctional materials. Transition metal doping is effective for sensitizing SrTiO3 under visible light. We have theoretically investigated the roles of the doped Cr in STO based on hybrid density-functional calculations. Cr atoms are preferably substituting for Ti under any equilibrium growth conditions. The lower oxidation state Cr3+, which is stabilized under an n-type condition of STO, is found to be advantageous for the photocatalytic performance. It is firther predicted that lanthanum is the best codopant for stabilizing the favorable oxidation state, Cr3+. The prediction was validated by our experiments that La and Cr co-doped STO shows the best performance among examined samples. This work was supported by the Japan Science and Technology Agency (JST) Precursory Research for Embryonic Science and Technology (PRESTO) and International Research Fellow program of Japan Society for the Promotion of Science (JSPS) through project P14207.

  3. Catalytic hydrogen/oxygen reaction assisted the proton exchange membrane fuel cell (PEMFC) startup at subzero temperature

    Science.gov (United States)

    Sun, Shucheng; Yu, Hongmei; Hou, Junbo; Shao, Zhigang; Yi, Baolian; Ming, Pingwen; Hou, Zhongjun

    Fuel cells for automobile application need to operate in a wide temperature range including freezing temperature. However, the rapid startup of a proton exchange membrane fuel cell (PEMFC) at subfreezing temperature, e.g., -20 °C, is very difficult. A cold-start procedure was developed, which made hydrogen and oxygen react to heat the fuel cell considering that the FC flow channel was the characteristic of microchannel reactor. The effect of hydrogen and oxygen reaction on fuel cell performance at ambient temperature was also investigated. The electrochemical characterizations such as I- V plot and cyclic voltammetry (CV) were performed. The heat generated rate for either the single cell or the stack was calculated. The results showed that the heat generated rate was proportional to the gas flow rate when H 2 concentration and the active area were constant. The fuel cell temperature rose rapidly and steadily by controlling gas flow rate.

  4. Graphene-based materials: fabrication, characterization and application for the decontamination of wastewater and wastegas and hydrogen storage/generation.

    Science.gov (United States)

    Wang, Hou; Yuan, Xingzhong; Wu, Yan; Huang, Huajun; Peng, Xin; Zeng, Guangming; Zhong, Hua; Liang, Jie; Ren, Miaomiao

    2013-07-01

    Graphene, as an ideal two-dimensional material and single-atom layer of graphite, has attracted exploding interests in multidisciplinary research because of its unique structure and exceptional physicochemical properties. Especially, graphene-based materials offer a wide range of potentialities for environmental remediation and energy applications. This review shows an extensive overview of the main principles and the recent synthetic technologies about designing and fabricating various innovative graphene-based materials. Furthermore, an extensive list of graphene-based sorbents and catalysts from vast literature has been compiled. The adsorptive and catalytic properties of graphene-based materials for the removal of various pollutants and hydrogen storage/production as available in the literature are presented. Tremendous adsorption capacity, excellent catalytic performance and abundant availability are the significant factors making these materials suitable alternatives for environmental pollutant control and energy-related system, especially in terms of the removal of pollutants in water, gas cleanup and purification, and hydrogen generation and storage. Meanwhile, a brief discussion is also included on the influence of graphene materials on the environment, and its toxicological effects. Lastly, some unsolved subjects together with major challenges in this germinating area of research are highlighted and discussed. Conclusively, the expanding of graphene-based materials in the field of adsorption and catalysis science represents a viable and powerful tool, resulting in the superior improvement of environmental pollution control and energy development. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Recent advances in hydrogen generation, distribution and control at Westinghouse

    International Nuclear Information System (INIS)

    Tsai, S.S.; Liparulo, N.J.; Srinivas, V.; Monty, B.S.

    1989-01-01

    This paper reports that since the TMI-2 accident, Westinghouse has been actively involved in an industry-wide effort to address the hydrogen issue. Westinghouse has developed and licensed the CLASIX and CLASIX-3 codes to utilities which own the PWR ice condenser plants and BWR Mark III plants. These utilities have used these codes to perform analyses to support a hydrogen mitigation system required by the NRC hydrogen control rule, 20CFR50.44. Lately, Westinghouse has made significant advances in the hydrogen control analysis method. The hydrogen control analysis methods newly developed by Westinghouse include: a fog inerting model; a detailed equipment survivability analysis model and criteria for survivability assessment; flame temperature criteria for air/steam/hydrogen mixtures; COMPACT: an advanced computer program for analysis of hydrogen behavior in containment and containment vent system. A methodology based on these analysis methods has been developed by Westinghouse to address all the hydrogen issues, including containment integrity during and after hydrogen burns, hydrogen detonation, potential for fog inerting, and equipment survivability

  6. Heterogeneous catalytic hydrogenation of biobased levulinic and succinic acids in aqueous solutions.

    Science.gov (United States)

    Corbel-Demailly, Louis; Ly, Bao-Khanh; Minh, Doan-Pham; Tapin, Benoit; Especel, Catherine; Epron, Florence; Cabiac, Amandine; Guillon, Emmanuelle; Besson, Michèle; Pinel, Catherine

    2013-12-01

    Supported noble-metal catalysts (Ru, Pd or Pt) and the corresponding Re-promoted catalysts exhibit a high activity for the hydrogenation of biobased carboxylic acids. Levulinic acid and succinic acid are converted into the lactones or the diols depending on the nature of the catalyst and the reaction conditions. The highest selectivity to 1,4-pentanediol of 82 % is achieved at 140 °C in the presence of the 1.9 % Ru-3.6 % Re/C catalyst. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Determination of the level of DNA modification with cisplatin by catalytic hydrogen evolution at mercury-based electrodes.

    Science.gov (United States)

    Horáková, Petra; Tesnohlídková, Lucie; Havran, Ludek; Vidláková, Pavlína; Pivonková, Hana; Fojta, Miroslav

    2010-04-01

    Electrochemical methods proved useful as simple and inexpensive tools for the analysis of natural as well as chemically modified nucleic acids. In particular, covalently attached metal-containing groups usually render the DNA well-pronounced electrochemical activity related to redox processes of the metal moieties, which can in some cases be coupled to catalytic hydrogen evolution at mercury or some types of amalgam electrodes. In this paper we used voltammetry at the mercury-based electrodes for the monitoring of DNA modification with cis-diamminedichloroplatinum (cisplatin), a representative of metallodrugs used in the treatment of various types of cancer or being developed for such purpose. In cyclic voltammetry at the mercury electrode, the cisplatin-modified DNA yielded catalytic currents the intensity of which reflected DNA modification extent. In square-wave voltammetry, during anodic polarization after prereduction of the cisplatinated DNA, a well-developed, symmetrical signal (peak P) was obtained. Intensity of the peak P linearly responded to the extent of DNA modification at levels relevant for biochemical studies (rb = 0.01-0.10, where rb is the number of platinum atoms bound per DNA nucleotide). We demonstrate a correlation between the peak P intensity and a loss of sequence-specific DNA binding by tumor suppressor protein p53, as well as blockage of DNA digestion by a restriction endonuclease Msp I (both caused by the DNA cisplatination). Application of the electrochemical technique in studies of DNA reactivity with various anticancer platinum compounds, as well as for an easy determination of the extent of DNA platination in studies of its biochemical effects, is discussed.

  8. DMFC at low air flow operation: Study of parasitic hydrogen generation

    International Nuclear Information System (INIS)

    Dohle, H.; Mergel, J.; Ghosh, P.C.

    2007-01-01

    In this paper, the effect of hydrogen generation in direct methanol fuel cells (DMFC) is described. Under certain operating conditions hydrogen generation occurs in DMFC causing an additional methanol consumption and a decrease of the cell voltage. For the present experiments a segmented cell with an active area of 244 cm 2 is used. The cell has 196 segments which are regularly distributed on the whole area. By this experimental setup hydrogen generation was found in regions with insufficient air supply. Hydrogen generation was analyzed by systematically applying different air flow rates and detecting the local current densities. The theory for hydrogen generation is confirmed by the results obtained from the segmented cell. A correlation between open circuit voltage (OCV), air flow rate and hydrogen generation was observed. Furthermore, half-cell measurements with different methanol concentrations were performed and used for analyzing the processes during hydrogen generation. The work clearly indicates the importance of sufficient cathode air supply for DMFC. Starved cathode areas not only do not contribute to the overall current generation but in addition reduce the power and efficiency by the parasitic generation of hydrogen

  9. Polyacrylonitrile Fibers Anchored Cobalt/Graphene Sheet Nanocomposite: A Low-Cost, High-Performance and Reusable Catalyst for Hydrogen Generation.

    Science.gov (United States)

    Zhang, Fei; Huang, Guoji; Hou, Chengyi; Wang, Hongzhi; Zhang, Qinghong; Li, Yaogang

    2016-06-01

    Cobalt and its composites are known to be active and inexpensive catalysts in sodium borohydride (NaBH4) hydrolysis to generate clean and renewable hydrogen energy. A novel fiber catalyst, cobalt/graphene sheet nanocomposite anchored on polyacrylonitrile fibers (Co/GRs-PANFs), which can be easily recycled and used in any reactor with different shapes, were synthesized by anchoring cobalt/graphene (Co/GRs) on polyacrylonitrile fibers coated with graphene (GRs-PANFs) at low temperature. The unique structure design effectively prevents the inter-sheet restacking of Co/GRs and fully exploits the large surface area of novel hybrid material for generate hydrogen. And the extra electron transfer path supplied by GRs on the surface of GRs-PANFs can also enhance their catalysis performances. The catalytic activity of the catalyst was investigated by the hydrolysis of NaBH4 in aqueous solution with GRs-PANFs. GRs powders and Co powders were used as control groups. It was found that both GRs and fiber contributed to the hydrogen generation rate of Co/GRs-PANFs (3222 mL x min(-1) x g(-1)), which is much higher than that of cobalt powders (915 mL x min(-1) x g(-1)) and Co/GRs (995 mL x min(-1) x g(-1)). The improved hydrogen generation rate, low cost and uncomplicated recycling make the Co/GRs-PANFs promising candidate as catalysts for hydrogen generation.

  10. Tuning of catalytic CO2 hydrogenation by changing composition of CuO–ZnO–ZrO2 catalysts

    International Nuclear Information System (INIS)

    Witoon, Thongthai; Kachaban, Nantana; Donphai, Waleeporn; Kidkhunthod, Pinit; Faungnawakij, Kajornsak; Chareonpanich, Metta

    2016-01-01

    Graphical abstract: The catalyst with an optimum composition of Cu:Zn:Zr (38.2:28.6:33.2) exhibited a homogeneous dispersion of metal components, and achieved the highest methanol yield. - Highlights: • A series of CuO–ZnO–ZrO 2 catalysts with different metal compositions were prepared. • Binary CuO–ZrO 2 catalyst exhibited higher methanol selectivity. • Increasing Zn/Cu ratios provided a better inter-dispersion of metal components. • The optimum catalyst composition of Cu–Zn–Zr (CZZ-4) was 38.2:28.6:33.2. • The CZZ-4 achieved the highest methanol yield (219.7 g CH3OH kg cat −1 h −1 ) at 240 °C. - Abstract: CO 2 hydrogenation was carried out over a series of CuO–ZnO–ZrO 2 catalysts prepared via a reverse co-precipitation method. The influence of catalyst compositions on the physicochemical properties of the catalysts as well as their catalytic performance was investigated. The catalysts were characterized by means of N 2 -sorption, X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), scanning electron microscopy (SEM), H 2 -temperature programmed reduction (H 2 -TPR), H 2 and CO 2 temperature-programmed desorption (H 2 - and CO 2 -TPD). The binary CuO–ZrO 2 (67:33) catalyst exhibits the highest methanol selectivity at all reaction temperature and its maximum yield of methanol (144.5 g methanol kg cat −1 h −1 ) is achieved at 280 °C, owing to the strong basic sites and the largest CuO crystallite size. The addition of Zn to the binary CuO–ZrO 2 catalyst causes a higher Cu dispersion and an increased number of active sites for CO 2 and H 2 adsorption. However, the basic strength of the ternary CuO–ZnO–ZrO 2 catalysts is lower than the binary CuO–ZrO 2 catalyst which provides the maximum yield of methanol at lower reaction tempertures (240 and 250 °C), depending on the catalyst compositions. The optimum catalyst composition of Cu–Zn–Zr (38.2:28.6:33.2) gives a superior methanol

  11. Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution

    International Nuclear Information System (INIS)

    Abbas, Syed Asad; Iqbal, Muhammad Ibrahim; Kim, Seong-Hoon; Jung, Kwang-Deog

    2017-01-01

    Highlights: • Urchin-like Ni is prepared in solvothermal reaction. • Urchin-like Ni is formed via Ni(OH) 2 aggregates in ethanol and oleylamine. • Exchange current density of urchin-like Ni is 0.191 mA cm −2 . • Urchin-like Ni exceeds the catalytic performance of commercial Pt/C in HER. - Abstract: Ni nanoparticles with different morphologies were synthesized for hydrogen evolution reaction (HER) in alkaline solution. Here, Ni(acac) 2 was converted into Ni metal nanoparticles in solvothermal reactions with simple alcohols and oleylamine (OAm). The morphology of the resulting Ni nanoparticles was dependent mainly on the OAm/Ni molar ratio in alcohol solvent. Aggregates of spherical Ni nanoparticles (NiEt-OAm1) were observed at the OAm/Ni molar ratio of 1.0, whereas two echinoid Ni nanoparticles (NiEt-OAm4 and NiEt-OAm6) could be prepared in ethanol at the OAm/Ni molar ratios of 4.0 and 6.0. Ni(OH) 2 formed in ethanol during a reaction time of 5 h was then reduced into echinoid Ni nanoparticles after 8 h. Echinoid Ni nanoparticles were formed by atomic addition on the tops of the multipod Ni particles formed via Ni(OH) 2 /NiO aggregates. Webbed feet-like particles (NiIPA-OAm4) with plate edges were also observed in isopropanol under the same reaction conditions. The catalytic activities of the prepared Ni nanoparticles for the hydrogen evolution reaction were evaluated in alkaline solution. The NiEt-OAm4 with urchin-like morphology was much more active than the NiIPA-OAm4 with webbed feet-like morphology. The exchange current density of Ni catalysts was increased with increasing the OAm/Ni molar ratio. The NiEt-OAm6 exhibited an exchange current of 0.191 mA cm −2 and the NiEt-OAm4 exceeded electrocatalytic performance of a commercial Pt catalysts (40% Pt on Vulcan XC 72) in a stability test for 100 kiloseconds at −1.5 V (vs. Hg/HgO) in 1.0 M NaOH due to its high stability.

  12. Catalytic Performance of Fe-Mn/SiO2 Nanocatalysts for CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mostafa Feyzi

    2013-01-01

    Full Text Available A series of x(Fe, Mn/SiO2 nanocatalysts (x=5, 10, 15, 20, 25, and 30 wt.% were prepared by sol-gel method and studied for the light olefins production from synthesis gas. It was found that the catalyst containing 20 wt.% (Fe, Mn/SiO2 is an optimal nano catalyst for production of C2–C4 olefins. Effects of sulfur treatment on the catalyst performance of optimal catalyst have been studied by espousing different volume fractions of H2S in a fixed bed stainless steel reactor. The results show that the catalyst treated with 6 v% of H2S had high catalytic performance for C2–C4 light olefins production. The best operational conditions were H2/CO = 3/2 molar feed ratio at 260°C and GHSV = 1100 h−1 under 1 bar total pressure. Characterization of catalysts was carried out using X-ray diffraction (XRD, scanning electron microscopy (SEM, transmission electron microscopy (TEM, and surface area measurements.

  13. Dependable Hydrogen and Industrial Heat Generation from the Next Generation Nuclear Plant

    Energy Technology Data Exchange (ETDEWEB)

    Charles V. Park; Michael W. Patterson; Vincent C. Maio; Piyush Sabharwall

    2009-03-01

    The Department of Energy is working with industry to develop a next generation, high-temperature gas-cooled nuclear reactor (HTGR) as a part of the effort to supply the US with abundant, clean and secure energy. The Next Generation Nuclear Plant (NGNP) project, led by the Idaho National Laboratory, will demonstrate the ability of the HTGR to generate hydrogen, electricity, and high-quality process heat for a wide range of industrial applications. Substituting HTGR power for traditional fossil fuel resources reduces the cost and supply vulnerability of natural gas and oil, and reduces or eliminates greenhouse gas emissions. As authorized by the Energy Policy Act of 2005, industry leaders are developing designs for the construction of a commercial prototype producing up to 600 MWt of power by 2021. This paper describes a variety of critical applications that are appropriate for the HTGR with an emphasis placed on applications requiring a clean and reliable source of hydrogen. An overview of the NGNP project status and its significant technology development efforts are also presented.

  14. Oxygen Mass Flow Rate Generated for Monitoring Hydrogen Peroxide Stability

    Science.gov (United States)

    Ross, H. Richard

    2002-01-01

    Recent interest in propellants with non-toxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because peroxide is sensitive to contaminants, material interactions, stability and storage issues, monitoring decomposition rates is important. Stennis Space Center (SSC) uses thermocouples to monitor bulk fluid temperature (heat evolution) to determine reaction rates. Unfortunately, large temperature rises are required to offset the heat lost into the surrounding fluid. Also, tank penetration to accomodate a thermocouple can entail modification of a tank or line and act as a source of contamination. The paper evaluates a method for monitoring oxygen evolution as a means to determine peroxide stability. Oxygen generation is not only directly related to peroxide decomposition, but occurs immediately. Measuring peroxide temperature to monitor peroxide stability has significant limitations. The bulk decomposition of 1% / week in a large volume tank can produce in excess of 30 cc / min. This oxygen flow rate corresponds to an equivalent temperature rise of approximately 14 millidegrees C, which is difficult to measure reliably. Thus, if heat transfer were included, there would be no temperature rise. Temperature changes from the surrounding environment and heat lost to the peroxide will also mask potential problems. The use of oxygen flow measurements provides an ultra sensitive technique for monitoring reaction events and will provide an earlier indication of an abnormal decomposition when compared to measuring temperature rise.

  15. Genetic defects of hydrogen peroxide generation in the thyroid gland.

    Science.gov (United States)

    Weber, G; Rabbiosi, S; Zamproni, I; Fugazzola, L

    2013-04-01

    Hydrogen peroxide (H2O2) is a key element in thyroid hormone biosynthesis. It is the substrate used by thyroid peroxidase for oxidation and incorporation of iodine into thyroglobulin, a process known as organification. The main enzymes composing the H2O2-generating system are the dual oxidase 2 (DUOX2) and the recently described DUOX maturation factor 2 (DUOXA2). Defects in these reactions lead to reduced thyroid hormone synthesis and hypothyroidism, with consequent increased TSH secretion and goiter. Since the first report in 2002 of DUOX2 mutations causing congenital hypothryoidism (CH), to date 25 different mutations have been described. Affected patients show a positive perchlorate discharge test and high phenotypic variability, ranging from transient to permanent forms of CH. Up to now, only two cases of CH due to DUOXA2 defects have been published. They also suggest the existence of a great genotype-phenotype variability. The phenotypic expression is probably influenced by genetic background and environmental factors. DUOX and DUOXA constitute a redundant system in which DUOX1/DUOXA1 can at least partially replace the function of DUOX2/DUOXA2. Furthermore, increased nutritional iodide could ensure a better use of H2O2 provided by DUOX1.

  16. Integrated photoelectrochemical energy storage: solar hydrogen generation and supercapacitor.

    Science.gov (United States)

    Xia, Xinhui; Luo, Jingshan; Zeng, Zhiyuan; Guan, Cao; Zhang, Yongqi; Tu, Jiangping; Zhang, Hua; Fan, Hong Jin

    2012-01-01

    Current solar energy harvest and storage are so far realized by independent technologies (such as solar cell and batteries), by which only a fraction of solar energy is utilized. It is highly desirable to improve the utilization efficiency of solar energy. Here, we construct an integrated photoelectrochemical device with simultaneous supercapacitor and hydrogen evolution functions based on TiO(2)/transition metal hydroxides/oxides core/shell nanorod arrays. The feasibility of solar-driven pseudocapacitance is clearly demonstrated, and the charge/discharge is indicated by reversible color changes (photochromism). In such an integrated device, the photogenerated electrons are utilized for H(2) generation and holes for pseudocapacitive charging, so that both the reductive and oxidative energies are captured and converted. Specific capacitances of 482 F g(-1) at 0.5 A g(-1) and 287 F g(-1) at 1 A g(-1) are obtained with TiO(2)/Ni(OH)(2) nanorod arrays. This study provides a new research strategy for integrated pseudocapacitor and solar energy application.

  17. General Tritium Labelling of Gentamicin C by catalytic hydrogen exchange Reaction with Tritiated Water

    International Nuclear Information System (INIS)

    Suarez, C.; Diaz, D.; Paz, D.

    1991-01-01

    Gentamicin C was labelled with tritium by means of a PtO2 catalyzed hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H2O-3H, and 50 mg of prereduced PtO2) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 degree celsius, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accomplished with a cellulose column eluted with the lower phase of chloroform-methanol 17 % ammonium hydroxide (2:1:1, v/v) . Chemical purity, determined by HPLC, was 96,5 % and radiochemical one was 95. Main exchange degradation products show biological activity. (Author) 12 refs

  18. Fabrication of porous boron-doped diamond electrodes by catalytic etching under hydrogen-argon plasma

    Science.gov (United States)

    Shi, Chao; Li, Cuiping; Li, Mingji; Li, Hongji; Dai, Wei; Wu, Yongheng; Yang, Baohe

    2016-01-01

    Porous boron-doped diamond (BDD) was prepared by hydrogen-argon plasma etching using electrodeposited Ni nanoparticles as a catalyst. The etching process and formation mechanism of porous BDD were investigated by changing the etching time from 30 s to 300 s. Pores were produced due to the C atoms around Ni nanoparticles are easy to react with hydrogen plasma and form methane. With the increase of etching time, the pore size increased, the pore density decreased, and the pore depth first increased and then maintained unchanged. The sp2-bonded graphitic carbons existing on the surface of BDD increase with increasing etching time due to the increase of surface area. No preferential etching was observed due to the high energy of argon plasma. The electrochemical behaviors of the pristine and porous BDD electrodes were characterized by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that the porous BDD electrode exhibited high specific capacitance, which is attributed to its high electrical conductivity and large specific surface area. The highest specific capacitance of porous BDD electrode is 9.55 mF cm-2, which is 22 times higher than that of pristine BDD electrode. The specific capacitance retention of the porous BDD electrode reduced to 98.2% of the initial capacitance after 500 cycles and then increased to 120.0% after 10,000 cycles. For the first 500 cycles, the reduction of capacitance can be attributed to the dissolution of Ni nanoparticles that attached on the porous BDD surface or buried in the shallow layer. The capacitance increase after 10,000 cycles is due to the better contact of the electrolytic solution with the residual Ni with the increase of cycle number.

  19. Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes

    KAUST Repository

    Sun, Xiaohui

    2017-11-20

    A supported cobalt catalyst with atomically dispersed Co-Nx sites (3.5 wt% Co) in a mesoporous N-doped carbon matrix (named Co@mesoNC) is synthesized by hydrolysis of tetramethyl orthosilicate (TMOS) in a Zn/Co bimetallic zeolitic imidazolate framework (BIMZIF(Co,Zn)), followed by high-temperature pyrolysis and SiO2 leaching. A combination of TEM, XRD XPS and X-ray absorption spectroscopy studies confirm the absence of cobalt nanoparticles and indicate that these highly dispersed cobalt species are present in the form of Co-Nx. The exclusive formation of Co-Nx sites in the carbon matrix is attributed to the presence of a large amount of Zn and N in the BIMZIF precursor together with the presence of SiO2 in the pore space of this framework, extending the initial spatial distance between cobalt atoms and thereby impeding their agglomeration. The presence of SiO2 during high-temperature pyrolysis is proven crucial to create mesoporosity and a high BET area and pore volume in the N-doped carbon support (1780 m2 g−1, 1.54 cm3 g−1). This heterogeneous Co@mesoNC catalyst displays high activity and selectivity (>99%) for the selective hydrogenation of nitrobenzene to aniline at mild conditions (0.5–3 MPa, 343–383 K). When more challenging substrates (functionalized nitroarenes) are hydrogenated, the catalyst Co@mesoNC displays an excellent chemoselectivity to the corresponding substituted anilines.The presence of mesoporosity improves mass transport of reactants and/or products and the accessibility of the active Co-Nx sites, and greatly reduces deactivation due to fouling.

  20. Construction and biofunctional evaluation of electrospun vascular graft loaded with selenocystamine for in situ catalytic generation of nitric oxide

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Siyuan; An, Jun; Weng, Lei [State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials for Ministry of Education, College of Life Sciences, Nankai University, Tianjin 300071 (China); Li, Yandong [Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071 (China); Xu, Han; Wang, Yaping; Ding, Dan; Kong, Deling [State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials for Ministry of Education, College of Life Sciences, Nankai University, Tianjin 300071 (China); Wang, Shufang, E-mail: wangshufang@nankai.edu.cn [State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials for Ministry of Education, College of Life Sciences, Nankai University, Tianjin 300071 (China)

    2014-12-01

    Construction and biofunctional evaluation of a novel vascular graft with in situ catalytic generation of nitric oxide were described in this paper. Poly α-lysine and poly (γ-glutamic acid) were deposited alternately onto the surface of an electrospun poly ε-caprolactone matrix via electrostatic layer-by-layer self-assembly, and then selenocystamine was loaded as a catalyst. Measurement of in vitro catalytic generation of nitric oxide demonstrated that this catalyst-loaded material could considerably accelerate the release of nitric oxide from S-nitrosoglutathione. A fibroblast proliferation assay showed that the material possessed satisfactory cellular compatibility. The catalyst-loaded material could inhibit the spread of smooth muscle cells in the presence of nitric oxide donors. In arteriovenous-shunt experiment, the catalyst-loaded graft exhibited good anti-thrombotic property where it could prevent acute thrombosis by decreasing the adhesion and activation of platelets and other blood cells. These data suggest a new method of building vascular grafts with improved hemocompatibility and biological functions. - Highlights: • A porous small-diameter vascular graft was prepared by electrospinning. • Selenocystamine was loaded for in situ catalytic and sustained NO generation. • There was a significant catalytic NO generation on the catalyst-loaded sample. • The spread of smooth muscle cells was inhibited on the catalyst-loaded sample. • The catalyst-loaded sample showed anti-thrombotic property in AV-shunt experiment.

  1. Influence of hydrogen bonding on the generation and stabilization of ...

    Indian Academy of Sciences (India)

    Keywords. Hydrogen bonding; polymer liquid crystals; smectic; thermal properties; polymer. ... The occurrence of the smectic phases in some of the polymers indicated possibly self-assembly through the formation of hetero intermolecular hydrogen bonded networks. A smectic polymorphism and in addition, ...

  2. Magnetic porous PtNi/SiO2 nanofibers for catalytic hydrogenation of p-nitrophenol

    Science.gov (United States)

    Guan, Huijuan; Chao, Cong; Kong, Weixiao; Hu, Zonggao; Zhao, Yafei; Yuan, Siguo; Zhang, Bing

    2017-06-01

    In this work, the mesoporous SiO2 nanofibers from pyrolyzing precursor of electrospun nanofibers were employed as support to immobilize PtNi nanocatalyst (PtNi/SiO2 nanofibers). AFM, XRD, SEM, TEM, XPS, ICP-AES and N2 adsorption/desorption analysis were applied to systematically investigate the morphology and microstructure of as-prepared products. Results showed that PtNi alloy nanoparticles with average diameter of 18.7 nm were formed and could be homogeneously supported on the surface of porous SiO2 nanofiber, which further indicated that the SiO2 nanofibers with well-developed porous structure, large specific surface area, and roughened surface was a benefit for the support of PtNi alloy nanoparticles. The PtNi/SiO2 nanofibers catalyst exhibited an excellent catalytic activity towards the reduction of p-nitrophenol, and the catalyst's kinetic parameter ( k n = 434 × 10-3 mmol s-1 g-1) was much higher than those of Ni/SiO2 nanofibers (18 × 10-3 mmol s-1 g-1), Pt/SiO2 nanofibers (55 × 10-3 mmol s-1 g-1) and previous reported PtNi catalysts. The catalyst could be easily recycled from heterogeneous reaction system based on its good magnetic properties (the Ms value of 11.48 emu g-1). In addition, PtNi/SiO2 nanofibers also showed an excellent stability and the conversion rate of p-nitrophenol still could maintain 94.2% after the eighth using cycle.

  3. Formation of polyhedral ceria nanoparticles with enhanced catalytic CO oxidation activity in thermal plasma via a hydrogen mediated shape control mechanism

    International Nuclear Information System (INIS)

    Zheng Jie; Zhang Yaohua; Song Xubo; Li Xingguo

    2011-01-01

    Ceria nanoparticles with well defined facets are prepared in argon–hydrogen thermal plasma followed by controlled oxidation. With increasing hydrogen fraction in the plasma, a clear sphere-to-polyhedron shape transition is observed. The heat released during the hydrogenation of cerium, which significantly enhances the species mobility on the surface, favors the growth of well defined facets. The polyhedron ceria nanoparticles, though lower in specific surface area, exhibit superior catalytic performance for CO oxidation over the round particles, which is attributed to the higher density of the reactive {200} and {220} facets on the surface. The hydrogen mediated shape control mechanism provides new insights into the shape control of nanoparticles during thermal plasma processing.

  4. Surface kinetics for catalytic combustion of hydrogen-air mixtures on platinum at atmospheric pressure in stagnation flows

    Science.gov (United States)

    Ikeda, H.; Sato, J.; Williams, F. A.

    1995-03-01

    Experimental studies of the combustion of premixed hydrogen-air mixtures impinging on the surface of a heated platinum plate at normal atmospheric pressure were performed and employed to draw inferences concerning surface reaction mechanisms and rate parameters applicable under practical conditions of catalytic combustion. Plate and gas temperatures were measured by thermocouples, and concentration profiles of major stable species in the gas were measured by gas-chromatographic analyses of samples withdrawn by quartz probes. In addition, ignition and extinction phenomena were recorded and interpreted with the aid of a heat balance at the surface and a previous flow-field analysis of the stagnation-point boundary layer. From the experimental and theoretical results, conclusions were drawn concerning the surface chemical-kinetic mechanisms and values of the elementary rate parameters that are consistent with the observations. In particular, the activation energy for the surface oxidation step H + OH → H 2O is found to be appreciably less at these high surface coverages than in the low-coverage limit.

  5. Kinetic spectrophotometric determination of Bi(III based on its catalytic effect on the oxidation of phenylfluorone by hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    SOFIJA M. RANČIĆ

    2009-08-01

    Full Text Available A new reaction was suggested and a new kinetic method was elaborated for determination of Bi(III in solution, based on its catalytic effect on the oxidation of phenyl-fluorone (PF by hydrogen peroxide in ammonia buffer. By application of spectrophotometric technique, a limit of quantification (LQ of 128 ng cm-3 was reached, and the limit of detection (LD of 37 ng cm-3 was obtained, where LQ was defined as the ratio signal:noise = 10:1 and LD was defined as signal 3:1 against the blank. The RSD value was found to be in the range 2.8–4.8 % for the investigated concentration range of Bi(III. The influence of some ions upon the reaction rate was tested. The method was confirmed by determining Bi(III in a stomach ulcer drug (“Bicit HP”, Hemofarm A.D.. The obtained results were compared to those obtained by AAS and good agreement of results was obtained.

  6. Rh nanoparticles supported on ultrathin carbon nanosheets for high-performance oxygen reduction reaction and catalytic hydrogenation.

    Science.gov (United States)

    Lin, Chong; Wu, Guanghao; Li, Huiqin; Geng, Yanmin; Xie, Gang; Yang, Jianhui; Liu, Bin; Jin, Jian

    2017-02-02

    We reported a facile and scalable salt-templated approach to produce monodisperse Rh nanoparticles (NPs) on ultrathin carbon nanosheets with the assistance of calcination under inert gas. More importantly, in spite of the essentially poor ORR activity of Rh/C, the acquired Rh/C hybrid nanosheets display a comparable ORR activity to the optimal commercial Pt/C catalyst, which may be due to the extra-small size of Rh NPs and the 2D defect-rich amorphous carbon nanosheets that can facilitate the charge transfer and reactive surface exposure. Moreover, Rh/C nanosheets present the optimal current density and best durability with the minimum decline during the entire test, so that ∼93% activity after 20 000 s is achieved, indicating a good lifetime for ORR. In contrast, commercial Pt/C and commercial Rh/C exhibited worse durability, so that ∼74% and ∼85% activities after 20 000 s are maintained. What's more, in the model system of reduction of 4-nitrophenol (4-NP), the kinetic constant k for Rh/C nanosheets is 3.1 × 10 -3 , which is 4.5 times than that of the commercial Rh/C catalyst, revealing that our Rh/C hybrid nanosheets can be potentially applied in industrial catalytic hydrogenation. This work opens a novel and facile way for the rest of the precious metal NPs to be supported on ultrathin carbon nanosheets for heterogeneous catalysis.

  7. Pyrolysis of de-oiled seed cake of Jatropha Curcas and catalytic steam reforming of pyrolytic bio-oil to hydrogen.

    Science.gov (United States)

    Renny, Andrew; Santhosh, Viswanathan; Somkuwar, Nitin; Gokak, D T; Sharma, Pankaj; Bhargava, Sanjay

    2016-11-01

    The aim of this work was to study the pyrolysis of de-oiled seed cake of Jatropha Curcas and catalytic steam reforming of pyrolytic bio-oil to hydrogen. As per literature, presence of heavy nitrogenous and oxygenated compounds leads to catalyst deactivation. Here, an attempt has been made to tune pyrolytic reactions to optimize the N and O content of the pyrolytic bio-oil. Bio-oil conversion and hydrogen yield decreased as reaction progressed, which attributes to temporary loss of catalytic activity by blockage of catalyst pores by carbon deposition. Further, retention of steam reforming activity after repetitive steam activation suggests long-term catalyst usage. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Catalytic reduction of 1,2-dihaloethanes by electrochemically generated C60n- (n=2 and 3)

    Science.gov (United States)

    D'Souza, F.; Choi, J.-P.; Hsieh, Y. Y.; Shriner, K.; Kutner, W.

    1998-08-01

    1,2-Dihaloethanes were catalytically reduced by electrochemically generated C60n- (n=2 or 3) anions in 0.1 M tetrabutlammonium hexafluorophosphate in benzonitrile under cyclic voltammetry and rotating disk electrode (RDE) voltammetry conditions at platinum electrodes. The second-order catalytic rate constants, determined by the RDE voltammetry under pseudo-first-order conditions against the 1,2-dihaloethanes, largely increase in the order: 1,2-dichloroethane1,2-dibromoethane<1,2-diiodoethane. Alkanes, alkenes and monohalogenated alkanes were products of the electrocatalyses.

  9. Catalytic Dehydrogenative Coupling of Hydrosilanes with Alcohols for the Production of Hydrogen On-demand: Application of a Silane/Alcohol Pair as a Liquid Organic Hydrogen Carrier.

    Science.gov (United States)

    Ventura-Espinosa, David; Carretero-Cerdán, Alba; Baya, Miguel; García, Hermenegildo; Mata, Jose A

    2017-08-10

    The compound [Ru(p-cym)(Cl) 2 (NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Method of generating hydrogen-storing hydride complexes

    Science.gov (United States)

    None, None

    2013-05-14

    A ternary hydrogen storage system having a constant stoichiometric molar ratio of LiNH.sub.2:MgH.sub.2:LiBH.sub.4 of 2:1:1. It was found that the incorporation of MgH.sub.2 particles of approximately 10 nm to 20 nm exhibit a lower initial hydrogen release temperature of 150.degree. C. Furthermore, it is observed that the particle size of LiBNH quaternary hydride has a significant effect on the hydrogen sorption concentration with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160.degree. C. and the other around 300.degree. C., with the main hydrogen release temperature reduced from 310.degree. C. to 270.degree. C., while hydrogen is first reversibly released at temperatures as low as 150.degree. C. with a total hydrogen capacity of 6 wt. % to 8 wt. %. Detailed thermal, capacity, structural and microstructural properties have been demonstrated and correlated with the activation energies of these materials.

  11. Functionalized cyclopentadienyl rhodium(III) bipyridine complexes: synthesis, characterization, and catalytic application in hydrogenation of ketones.

    Science.gov (United States)

    Wang, Wan-Hui; Suna, Yuki; Himeda, Yuichiro; Muckerman, James T; Fujita, Etsuko

    2013-07-14

    A series of highly functionalized cyclopentadienyl rhodium(III) complexes, [Cp'Rh(bpy)Br](ClO4) (Cp' = substituted cyclopentadienyl), was synthesized from various multi-substituted cyclopentadienes (Cp'H). [Rh(cod)Cl]2 and Cp'H were firstly converted to [Cp'Rh(cod)] complexes, which were then treated with Br2 to give the rhodium(III) dibromides [Cp'RhBr2]2. The novel complexes [Cp'Rh(bpy)Br](ClO4) were obtained readily by the reaction of 2,2'-bipyridine with [Cp'RhBr2]2. These rhodium complexes [Cp'Rh(bpy)Br](ClO4) were fully characterized and utilized in the hydrogenation of cyclohexanone and acetophenone with generally high yields, but they did not exhibit the same reactivity trends for the two substrate ketones. The different activity of these complexes for the different substrates may be due to the influence of the substituents on the Cp' rings.

  12. Model Catalytic Studies of Novel Liquid Organic Hydrogen Carriers: Indole, Indoline and Octahydroindole on Pt(111).

    Science.gov (United States)

    Schwarz, Matthias; Bachmann, Philipp; Silva, Thais Nascimento; Mohr, Susanne; Scheuermeyer, Marlene; Späth, Florian; Bauer, Udo; Düll, Fabian; Steinhauer, Johann; Hohner, Chantal; Döpper, Tibor; Noei, Heshmat; Stierle, Andreas; Papp, Christian; Steinrück, H-P; Wasserscheid, Peter; Görling, Andreas; Libuda, Jörg

    2017-10-20

    Indole derivatives were recently proposed as potential liquid organic hydrogen carriers (LOHC) for storage of renewable energies. In this work, we have investigated the adsorption, dehydrogenation and degradation mechanisms in the indole/indoline/octahydroindole system on Pt(111). We have combined infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS) and DFT calculations. Indole multilayers show a crystallization transition at 200 K, in which the molecules adopt a strongly tilted orientation, before the multilayer desorbs at 220 K. For indoline, a less pronounced restructuring transition occurs at 150 K and multilayer desorption is observed at 200 K. Octahydroindole multilayers desorb already at 185 K, without any indication for restructuring. Adsorbed monolayers of all three compounds are stable up to room temperature and undergo deprotonation at the NH bond above 300 K. For indoline, the reaction is followed by partial dehydrogenation at the 5-membered ring, leading to the formation of a flat-lying di-σ-indolide in the temperature range from 330-390 K. Noteworthy, the same surface intermediate is formed from indole. In contrast, the reaction of octahydroindole with Pt(111) leads to the formation of a different intermediate, which originates from partial dehydrogenation of the 6-membered ring. Above 390 K, all three compounds again form the same strongly dehydrogenated and partially decomposed surface species. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Improving the catalytic activity of amorphous molybdenum sulfide for hydrogen evolution reaction using polydihydroxyphenylalanine modified MWCNTs

    Science.gov (United States)

    Li, Maoguo; Yu, Muping; Li, Xiang

    2018-05-01

    Molybdenum sulfides are promising electrocatalysts for hydrogen evolution reaction (HER) in acid medium due to their unique properties. In order to improve their HER activity, different strategies have been developed. In this study, amorphous molybdenum sulfide was prepared by a simple wet chemical method and its HER activity was further improved by using polydihydroxyphenylalanine (PDOPA) modified MWCNTs as supports. It was found that the PDOPA can effectively improve the hydrophilic properties of multiwalled carbon nanotubes (MWCNTs) and amorphous MoSx can uniformly grow on the surface of PDOPA@MWCNTs. Compared with MoSx and MoSx/MWCNTs, MoSx/PDOPA@MWCNTs show obviously enhanced HER activities due to the superior electrical conductivity and more exposed active sites. In addition, the effect of the ratio of MoSx and PDOPA@MWCNTs and the loading amount of catalysts on the electrodes are also investigated in detail. At the optimum conditions, MoSx/PDOPA@MWCNTs display an overpotential of 198 mV at 10 mA/cm2, a Tafel slope of 53 mV/dec and a good long-term stability in 0.5 M H2SO4, which make them promising candidates for HER application.

  14. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant

    Directory of Open Access Journals (Sweden)

    Mukhamad Nurhadi

    2017-04-01

    Full Text Available The modified coal char from low-rank coal by sulfonation, titanium impregnation and followed by alkyl silylation possesses high catalytic activity in styrene oxidation. The surface of coal char was undergone several steps as such: modification using concentrated sulfuric acid in the sulfonation process, impregnation of 500 mmol titanium(IV isopropoxide and followed by alkyl silylation of n-octadecyltriclorosilane (OTS. The catalysts were characterized by X-ray diffraction (XRD, IR spectroscopy, nitrogen adsorption, and hydrophobicity. The catalytic activity of the catalysts has been examined in the liquid phase styrene oxidation by using aqueous hydrogen peroxide as oxidant. The catalytic study showed the alkyl silylation could enhance the catalytic activity of Ti-SO3H/CC-600(2.0. High catalytic activity and reusability of the o-Ti-SO3H/CC-600(2.0 were related to the modification of local environment of titanium active sites and the enhancement the hydrophobicity of catalyst particle by alkyl silylation. Copyright © 2017 BCREC GROUP. All rights reserved Received: 24th May 2016; Revised: 11st October 2016; Accepted: 18th October 2016 How to Cite: Nurhadi, M. (2017. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 55-61 (doi:10.9767/bcrec.12.1.501.55-61 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.501.55-61

  15. Feasibility study of hydrogen generator with molten slag granulation

    Energy Technology Data Exchange (ETDEWEB)

    Akiyama, T.; Mizuochi, T. [Graduate School of Engineering, Osaka Pref. Univ., Sakai, Osaka (Japan); Yagi, J.I.; Nogami, H. [Inst. of Multidisciplinary Research for Advanced Materials, Tohoku Univ., Aobaku, Sendai (Japan)

    2004-02-01

    A huge amount of hot molten oxides, such as steelmaking slag and molten municipal waste, is discharged at present without heat recovery, in spite of its very high potential. For example, hot molten slag as a byproduct in the Japanese steelmaking industry, over 1723 K in temperature, reaches as much as 30 million tonnes annually. To recover heat of the viscous slag chemically, the strongly endothermic reaction CH{sub 4}+H{sub 2}O {yields} 3H{sub 2}+CO was selected and then the property of dry granulation of the molten slag by rotary cup atomizer (RCA) for expanding surface area of the slag was experimentally studied. The purpose of this paper was, therefore, to study slag granulation under various conditions for promoting heat exchange between slag and gas, in which the influence of the rotating speed and the shape of the cup on the slag drop size was mainly examined. The collected slag drops were correlated with operating conditions such as rotating speed, cup shape, etc. Most significantly, the molten slag was successfully granulated under the dry conditions without water impingement. The rotating speed of the cup influenced the diameter and shape of the slag drops very strongly. The higher rotating speed made the slag drops smaller, more spherical and uniform. Drops with 5 to 6 mm of average dimension were obtained at a rotating speed of 15 rps (900 rpm), and drops with about 1 mm at 50 rps (3000 rpm). In the former case, the shape of the obtained drops changed from spherical to ribbon-like. These results will be useful to establish new heat recovery processes with hydrogen generation from molten slag with many benefits. Energy analysis and cost evaluation were also conducted, to study the benefit of the proposed process. (orig.)

  16. Photocatalytic hydrogen generation from water with iron carbonyl phosphine complexes: improved water reduction catalysts and mechanistic insights.

    Science.gov (United States)

    Gärtner, Felix; Boddien, Albert; Barsch, Enrico; Fumino, Koichi; Losse, Sebastian; Junge, Henrik; Hollmann, Dirk; Brückner, Angelika; Ludwig, Ralf; Beller, Matthias

    2011-05-27

    An extended study of a novel visible-light-driven water reduction system containing an iridium photosensitizer, an in situ iron(0) phosphine water reduction catalyst (WRC), and triethylamine as sacrificial reductant is described. The influences of solvent composition, ligand, ligand-to-metal ratio, and pH were studied. The use of monodentate phosphine ligands led to improved activity of the WRC. By applying a WRC generated in situ from Fe(3) (CO)(12) and tris[3,5-bis(trifluoromethyl)phenyl]phosphine (P[C(6)H(3)(CF(3))(2)](3), Fe(3)(CO)(12)/PR(3)=1:1.5), a catalyst turnover number of more than 1500 was obtained, which constitutes the highest activity reported for any Fe WRC. The maximum incident photon to hydrogen efficiency obtained was 13.4% (440 nm). It is demonstrated that the evolved H(2) flow (0.23 mmol H(2) h(-1) mg(-1) Fe(3)(CO)(12)) is sufficient to be used in polymer electrolyte membrane fuel cells, which generate electricity directly from water with visible light. Mechanistic studies by NMR spectroscopy, in situ IR spectroscopy, and DFT calculations allow for an improved understanding of the mechanism. With respect to the Fe WRC, the complex [HNEt(3)](+)[HFe(3)(CO)(11)](-) was identified as the key intermediate during the catalytic cycle, which led to light-driven hydrogen generation from water. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Green diesel production via catalytic hydrogenation/decarboxylation of triglycerides and fatty acids of vegetable oil and brown grease

    Science.gov (United States)

    Sari, Elvan

    than activated carbon itself for both decarboxylation of oleic acid and hydrogenation of alkenes. In an additional effort to reduce Pd amount in the catalyst, Pd2Co/C catalysts with various Pd content were prepared and the catalytic activity study showed that 0.5 wt% Pd2Co/C catalyst performs even better than a 5 wt% Pd/C catalyst. Pd and Co alloys were very well dispersed and formed fine clusters, which led to a higher active metal surface area and hence favored the decarboxylation of oleic acid. This study showed that an alloy of Pd on carbon with a significantly low Pd content is much more active and selective to diesel hydrocarbons production from an unsaturated fatty acid in super-critical water and may be regarded as a prospective feasible decarboxylation catalyst for the removal of oxygen from vegetable oil/animal fat without the need of additional hydrogen.

  18. Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

    Science.gov (United States)

    Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

    2015-07-14

    Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

  19. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights.

    Science.gov (United States)

    Mellmann, Dörthe; Barsch, Enrico; Bauer, Matthias; Grabow, Kathleen; Boddien, Albert; Kammer, Anja; Sponholz, Peter; Bentrup, Ursula; Jackstell, Ralf; Junge, Henrik; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2014-10-13

    The iron-catalyzed dehydrogenation of formic acid has been studied both experimentally and mechanistically. The most active catalysts were generated in situ from cationic Fe(II) /Fe(III) precursors and tris[2-(diphenylphosphino)ethyl]phosphine (1, PP3 ). In contrast to most known noble-metal catalysts used for this transformation, no additional base was necessary. The activity of the iron catalyst depended highly on the solvent used, the presence of halide ions, the water content, and the ligand-to-metal ratio. The optimal catalytic performance was achieved by using [FeH(PP3 )]BF4 /PP3 in propylene carbonate in the presence of traces of water. With the exception of fluoride, the presence of halide ions in solution inhibited the catalytic activity. IR, Raman, UV/Vis, and EXAFS/XANES analyses gave detailed insights into the mechanism of hydrogen generation from formic acid at low temperature, supported by DFT calculations. In situ transmission FTIR measurements revealed the formation of an active iron formate species by the band observed at 1543 cm(-1) , which could be correlated with the evolution of gas. This active species was deactivated in the presence of chloride ions due to the formation of a chloro species (UV/Vis, Raman, IR, and XAS). In addition, XAS measurements demonstrated the importance of the solvent for the coordination of the PP3 ligand. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Hydrogen Generator by Methane Pyrolysis with Carbon Capture, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — ORBITEC proposes to develop, fabricate, and test a system to provide 99.999% hydrogen by efficiently performing methane pyrolysis. The system has three unique...

  1. Steam generators of Phenix: Measurement of the hydrogen concentration in sodium for detecting water leaks in the steam generator tubes

    International Nuclear Information System (INIS)

    Cambillard, E.; Lacroix, A.; Langlois, J.; Viala, J.

    1975-01-01

    The Phenix secondary circuits are provided with measurement systems of hydrogen concentration in sodium, that allow for the detection of possible water leaks in steam generators and the location of a faulty module. A measurement device consists of : a detector with nickel membranes of 0, 3 mm wall thickness, an ion pump with a 200 l/s flow rate, a quadrupole mass spectrometer and a calibrated hydrogen leak. The temperature correction is made automatically. The main tests carried out on the leak detection systems are reported. Since the first system operation (October 24, 1973), the measurements allowed us to obtain the hydrogen diffusion rates through the steam generator tube walls. (author)

  2. Catalytic thermometric titrations in non-aqueous solvents by coulometrically generated titrant.

    Science.gov (United States)

    Vajgand, V J; Gaál, F F; Brusin, S S

    1970-05-01

    Catalytic thermometric titrations have been developed for tertiary amines and salts of organic acids in acetic and propionic anhydride with titrant coulometrically generated at a mercury and/or platinum anode, hydroquinone being added to the solution titrated if the platinum anode is used. The results obtained are compared with those obtained by coulometric titration with the end-point detected either photometrically or potentiometrically. On a élaboré des titrages thermométriques catalytiques pour les amines tertiaires et les sels d'acides organiques en anhydrides aétique et propionique avec l'agent de titrage engendré coulométriquement sur une anode de mercure et/ou platine, de l'hydroquinone étant ajoutée à la solution titrée si l'on emploie l'anode de platine. Les résultats obtenus sont comparés avec ceux obtenus par titrage coulométrique avec le point de fin de réaction détecté soit photométriquement soit potentioétriquement.

  3. On Board Hydrogen Generation for Fuel Cell Powered Electric Cars. a Review of Various Available Techniques Production d'hydrogène embarquée pour véhicules électriques à piles. Aperçu de différentes techniques envisageables

    OpenAIRE

    Prigent M.

    2006-01-01

    Various methods allowing onboard hydrogen generation for fuel cell powered electric cars are reviewed. The following primary fuels are considered : ammonia, methanol, ethanol, and hydrocarbons. The catalytic cracking of ammonia allows generation of a CO2-free mixture containing 75% hydrogen, which is consequently suitable without subsequent purification for the supply of alkaline fuel cells. The problems posed by this primary fuel are toxicity in the event of leaks and the risk of generating ...

  4. Activation of the C-H bond: catalytic hydroxylation of hydrocarbons by new cobaltic alkylperoxydic complexes; selective and catalytic cycloalkane dehydrogenation in presence of uranium for hydrogen transfer

    International Nuclear Information System (INIS)

    Brazi, E.

    1987-01-01

    The aim of the thesis is to improve efficiency and selectivity of chemical reactions for alkane transformations. In the first part decomposition of hydroperoxides and hydrocarbon hydroxylation by cobalt complexes is studied. In the second part cycloalkanes are dehydrogenated into aromatics with a Pt catalyst, trapping hydrogen by uranium. Uranium hydride UH 3 can yield very pure hydrogen at reasonable temperature [fr

  5. Cyanogel-derived N-doped C nanosheets immobilizing Pd-P nanoparticles: One-pot synthesis and enhanced hydrogenation catalytic performance

    Science.gov (United States)

    Zhang, Hao; Yan, Xiaohong; Huang, Yundi; Zhang, Mengru; Tang, Yawen; Sun, Dongmei; Xu, Lin; Wei, Shaohua

    2017-02-01

    For Pd-based nanocatalysts, stabilization of Pd nanoparticles on carbon support could not only effectively avoid particle aggregation and maintain catalytic stability during catalytic processes, but also facilitate enhancing the catalytic activity due to the synergy between Pd nanoparticles and carbon support. Furthermore, the incorporation of non-metal of phosphorus (P) into Pd could effectively modulate the electronic structure of Pd and thus help to boost the catalytic properties. However, one-pot synthesis of such nanohybrids remains a great challenge due to the distinct physiochemical properties of Pd, P and C components. Herein, we demonstrate a one-pot and scalable synthesis of highly dispersed PdP alloy nanoparticle-immobilized on N-doped graphitic carbon nanosheets (abbreviated as Pd-P@N-C nanosheets) by using inorganic-organic hybrid cyanogel as a reaction precursor. In virtue of both compositional and structural advantages, the as-synthesized Pd-P@N-C nanosheets manifest a superior catalytic activity and stability toward the hydrogenation of 4-nitrophenol (4-NP). We believe that the present work will provide a feasible and versatile strategy for the development of efficient catalysts for environmental remediation and can also be extendable to other carbon-based nanohybrids with desirable functionalities.

  6. Probing Hot Electron Flow Generated on Pt Nanoparticles with Au/TiO2 Schottky Diodes during Catalytic CO Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jeong Y.; Lee, Hyunjoo; Renzas, J. Russell; Zhang, Yawen; Somorjai, G.A.

    2008-05-01

    Hot electron flow generated on colloid platinum nanoparticles during exothermic catalytic carbon monoxide oxidation was directly detected with Au/TiO{sub 2} diodes. Although Au/TiO{sub 2} diodes are not catalytically active, platinum nanoparticles on Au/TiO{sub 2} exhibit both chemicurrent and catalytic turnover rate. Hot electrons are generated on the surface of the metal nanoparticles and go over the Schottky energy barrier between Au and TiO{sub 2}. The continuous Au layer ensures that the metal nanoparticles are electrically connected to the device. The overall thickness of the metal assembly (nanoparticles and Au thin film) is comparable to the mean free path of hot electrons, resulting in ballistic transport through the metal. The chemicurrent and chemical reactivity of nanoparticles with citrate, hexadecylamine, hexadecylthiol, and TTAB (Tetradecyltrimethylammonium Bromide) capping agents were measured during catalytic CO oxidation at pressures of 100 Torr O{sub 2} and 40 Torr CO at 373-513 K. We found that chemicurrent yield varies with each capping agent, but always decreases with increasing temperature. We suggest that this inverse temperature dependence is associated with the influence of charging effects due to the organic capping layer during hot electron transport through the metal-oxide interface.

  7. Solar Photo Catalytic Hydrogen Production from water using a dual bed photosystem

    Energy Technology Data Exchange (ETDEWEB)

    Florida Solar Energy Center

    2003-03-30

    A body of work was performed in which the feasibility of photocatalytically decomposing water into its constituent elements using a dual bed, or modular photosystem, under solar radiation was investigated. The system envisioned consists of two modules, each consisting of a shallow, flat, sealed container, in which microscopic photocatalytic particles are immobilized. The photocatalysts absorb light, generating free electrons and lattice vacancy holes, which are capable of performing reductive and oxidative chemistry, respectively. The photocatalysts would be chosen as to whether they specifically promote H{sub 2} or O{sub 2} evolution in their respective containers. An aqueous solution containing a redox mediator is pumped between the two chambers in order to transfer electron equivalents from one reaction to the other.

  8. Next Generation Hybrid Photo-Catalytic Oxidation (PCO) for Trace Contaminant Control

    Data.gov (United States)

    National Aeronautics and Space Administration — Photocatalytic oxidation (PCO) is a primary candidate as an alternative to thermal-catalytic or sorbent- based technologies for VOC trace contaminant control due to...

  9. Hydrogen production by steam reforming of bio-alcohols. The use of conventional and membrane-assisted catalytic reactors

    Energy Technology Data Exchange (ETDEWEB)

    Seelam, P. K.

    2013-11-01

    The energy consumption around the globe is on the rise due to the exponential population growth and urbanization. There is a need for alternative and non-conventional energy sources, which are CO{sub 2}-neutral, and a need to produce less or no environmental pollutants and to have high energy efficiency. One of the alternative approaches is hydrogen economy with the fuel cell (FC) technology which is forecasted to lead to a sustainable society. Hydrogen (H{sub 2}) is recognized as a potential fuel and clean energy carrier being at the same time a carbon-free element. Moreover, H{sub 2} is utilized in many processes in chemical, food, metallurgical, and pharmaceutical industry and it is also a valuable chemical in many reactions (e.g. refineries). Non-renewable resources have been the major feedstock for H{sub 2} production for many years. At present, {approx}50% of H{sub 2} is produced via catalytic steam reforming of natural gas followed by various down-stream purification steps to produce {approx}99.99% H{sub 2}, the process being highly energy intensive. Henceforth, bio-fuels like biomass derived alcohols (e.g. bio-ethanol and bio-glycerol), can be viable raw materials for the H{sub 2} production. In a membrane based reactor, the reaction and selective separation of H{sub 2} occur simultaneously in one unit, thus improving the overall reactor efficiency. The main motivation of this work is to produce H{sub 2} more efficiently and in an environmentally friendly way from bio-alcohols with a high H{sub 2} selectivity, purity and yield. In this thesis, the work was divided into two research areas, the first being the catalytic studies using metal decorated carbon nanotube (CNT) based catalysts in steam reforming of ethanol (SRE) at low temperatures (<450 deg C). The second part was the study of steam reforming (SR) and the water-gas-shift (WGS) reactions in a membrane reactor (MR) using dense and composite Pd-based membranes to produce high purity H{sub 2}. CNTs

  10. Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

    Science.gov (United States)

    Rhodes, Christopher P. (Inventor); Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Anderson, Kelvin C. (Inventor)

    2011-01-01

    A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

  11. A conserved hydrogen-bond network in the catalytic centre of animal glutaminyl cyclases is critical for catalysis.

    Science.gov (United States)

    Huang, Kai-Fa; Wang, Yu-Ruei; Chang, En-Cheng; Chou, Tsung-Lin; Wang, Andrew H-J

    2008-04-01

    QCs (glutaminyl cyclases; glutaminyl-peptide cyclotransferases, EC 2.3.2.5) catalyse N-terminal pyroglutamate formation in numerous bioactive peptides and proteins. The enzymes were reported to be involved in several pathological conditions such as amyloidotic disease, osteoporosis, rheumatoid arthritis and melanoma. The crystal structure of human QC revealed an unusual H-bond (hydrogen-bond) network in the active site, formed by several highly conserved residues (Ser(160), Glu(201), Asp(248), Asp(305) and His(319)), within which Glu(201) and Asp(248) were found to bind to substrate. In the present study we combined steady-state enzyme kinetic and X-ray structural analyses of 11 single-mutation human QCs to investigate the roles of the H-bond network in catalysis. Our results showed that disrupting one or both of the central H-bonds, i.e., Glu(201)...Asp(305) and Asp(248)...Asp(305), reduced the steady-state catalysis dramatically. The roles of these two COOH...COOH bonds on catalysis could be partly replaced by COOH...water bonds, but not by COOH...CONH(2) bonds, reminiscent of the low-barrier Asp...Asp H-bond in the active site of pepsin-like aspartic peptidases. Mutations on Asp(305), a residue located at the centre of the H-bond network, raised the K(m) value of the enzyme by 4.4-19-fold, but decreased the k(cat) value by 79-2842-fold, indicating that Asp(305) primarily plays a catalytic role. In addition, results from mutational studies on Ser(160) and His(319) suggest that these two residues might help to stabilize the conformations of Asp(248) and Asp(305) respectively. These data allow us to propose an essential proton transfer between Glu(201), Asp(305) and Asp(248) during the catalysis by animal QCs.

  12. Investment in hydrogen tri-generation for wastewater treatment plants under uncertainties

    Science.gov (United States)

    Gharieh, Kaveh; Jafari, Mohsen A.; Guo, Qizhong

    2015-11-01

    In this article, we present a compound real option model for investment in hydrogen tri-generation and onsite hydrogen dispensing systems for a wastewater treatment plant under price and market uncertainties. The ultimate objective is to determine optimal timing and investment thresholds to exercise initial and subsequent options such that the total savings are maximized. Initial option includes investment in a 1.4 (MW) Molten Carbonate Fuel Cell (MCFC) fed by mixture of waste biogas from anaerobic digestion and natural gas, along with auxiliary equipment. Produced hydrogen in MCFC via internal reforming, is recovered from the exhaust gas stream using Pressure Swing Adsorption (PSA) purification technology. Therefore the expansion option includes investment in hydrogen compression, storage and dispensing (CSD) systems which creates additional revenue by selling hydrogen onsite in retail price. This work extends current state of investment modeling within the context of hydrogen tri-generation by considering: (i) Modular investment plan for hydrogen tri-generation and dispensing systems, (ii) Multiple sources of uncertainties along with more realistic probability distributions, (iii) Optimal operation of hydrogen tri-generation is considered, which results in realistic saving estimation.

  13. Effect of hydrogen on the growth and morphology of single wall carbon nanotubes synthesized on a Fe-Mo/MgO catalytic system

    Energy Technology Data Exchange (ETDEWEB)

    Biris, Alexandru R. [National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj Napoca, RO-3400 (Romania)], E-mail: biris@oc1.itim-cj.ro; Li Zhongrui; Dervishi, Enkeleda [Applied Science Department, University of Arkansas at Little Rock, 2801 S. University Ave, Little Rock, AR 72204 (United States); Nanotechnology Center, University of Arkansas at Little Rock, 2801 S. University Ave, Little Rock, AR 72204 (United States); Lupu, Dan [National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj Napoca, RO-3400 (Romania); Xu Yang; Saini, Viney [Applied Science Department, University of Arkansas at Little Rock, 2801 S. University Ave, Little Rock, AR 72204 (United States); Nanotechnology Center, University of Arkansas at Little Rock, 2801 S. University Ave, Little Rock, AR 72204 (United States); Watanabe, Fumiya [Nanotechnology Center, University of Arkansas at Little Rock, 2801 S. University Ave, Little Rock, AR 72204 (United States); Biris, Alexandru S. [Applied Science Department, University of Arkansas at Little Rock, 2801 S. University Ave, Little Rock, AR 72204 (United States); Nanotechnology Center, University of Arkansas at Little Rock, 2801 S. University Ave, Little Rock, AR 72204 (United States)], E-mail: asbiris@ualr.edu

    2008-04-21

    Single wall carbon nanotubes were synthesized from thermal pyrolysis of methane on a Fe-Mo/MgO catalyst by radio frequency catalytic chemical vapor deposition (RF-CVD) using argon as a carrier gas. Controlled amounts of hydrogen (H{sub 2}/CH{sub 4}=0-1 v/v) were introduced in separate experiments along with the carbon source. The properties and morphology of the synthesized single wall carbon nanotubes were monitored by transmission electron microscopy, Raman scattering, and thermogravimetric analysis. The nanotubes with the highest crystallinity were obtained with H{sub 2}/CH{sub 4}=0.6. By monitoring the Radial Breathing Modes present in the Raman spectra of the single-wall carbon nanotube samples, the variation of the structural and morphological properties of the carbon nanotubes with the flow level of hydrogen, reflect changes of the catalyst systems induced by the presence of hydrogen.

  14. Autothermal hydrogen storage and delivery systems

    Science.gov (United States)

    Pez, Guido Peter [Allentown, PA; Cooper, Alan Charles [Macungie, PA; Scott, Aaron Raymond [Allentown, PA

    2011-08-23

    Processes are provided for the storage and release of hydrogen by means of dehydrogenation of hydrogen carrier compositions where at least part of the heat of dehydrogenation is provided by a hydrogen-reversible selective oxidation of the carrier. Autothermal generation of hydrogen is achieved wherein sufficient heat is provided to sustain the at least partial endothermic dehydrogenation of the carrier at reaction temperature. The at least partially dehydrogenated and at least partially selectively oxidized liquid carrier is regenerated in a catalytic hydrogenation process where apart from an incidental employment of process heat, gaseous hydrogen is the primary source of reversibly contained hydrogen and the necessary reaction energy.

  15. Utilization of hydrogen gas production for electricity generation in ...

    African Journals Online (AJOL)

    Enterobacter aerogenes ADH-43 is a hydrogen gas (H2) producing mutant bacterium and a facultative anaerobic microbe. This double mutant was obtained by classical mutagenetically treated in order to enhance H2 production. In addition, this mutant has ability to degrade molasses from sugar factory as well as other ...

  16. Combustion of hydrogen-oxygen mixture in electrochemically generated nanobubbles

    NARCIS (Netherlands)

    Svetovoy, Vitaly; Sanders, Remco G.P.; Lammerink, Theodorus S.J.; Elwenspoek, Michael Curt

    2011-01-01

    Ignition of exothermic chemical reactions in small volumes is considered as difficult or impossible due to the large surface-to-volume ratio. Here observation of the spontaneous reaction is reported between hydrogen and oxygen in bubbles whose diameter is smaller than a threshold value around 150

  17. Solar-hydrogen generation and solar concentration (Conference Presentation)

    NARCIS (Netherlands)

    Sulima, Oleg V.; Chinello, Enrico; Conibeer, Gavin; Modestino, Miquel A.; Schüttauf, Jan-Willem; Lambelet, David; Delfino, Antonio; Domine, Didier; Faes, Antonin; Despeisse, Matthieu; Bailat, Julien; Psaltis, Demetri; Fernandez Rivas, David; Ballif, Christophe; Moser, Christophe

    2016-01-01

    We successfully demonstrated and reported the highest solar-to-hydrogen efficiency with crystalline silicon cells and Earth-abundant electrocatalysts under unconcentrated solar radiation. The combination of hetero-junction silicon cells and a 3D printed Platinum/Iridium-Oxide electrolyzer has been

  18. Influence of hydrogen bonding on the generation and stabilization of ...

    Indian Academy of Sciences (India)

    ety totally vanquished liquid crystalline phases while biphenylene and naphthalene units did only reduce the transition .... firms the fact that during heating some of the amide–ester hydrogen bonds change into amide–amide ... their potential applications in LC displays, NLO materials, information storage devices etc. [12].

  19. Analysis of Hydrogen Generation and Accumulation in U-233 Tube Vaults

    International Nuclear Information System (INIS)

    Ally, M.R.; Willis, K.J.

    1999-01-01

    The purpose of the 233 U Safe Storage Program is to enhance the safe storage of 233 U-bearing materials. This report describes the work done at the Oak Ridge National Laboratory's Radiochemical Development Facility (RDF) to address questions related to possible hydrogen generation and accumulation in 233 U tube vaults. The objective of this effort was to verify assumptions in the mathematical model used to estimate the hydrogen content of the gaseous atmosphere that possibly could occur inside the tube vaults in Building 3019 and to evaluate proposed measures for mitigating any hydrogen concerns. A mathematical model was developed using conservative assumptions to evaluate possible hydrogen generation and accumulation in the tube vaults. The model concluded that an equilibrium concentration would be established below the lower flammability limit (LFL) of 4.1% hydrogen. The major assumptions used in the model that were validated are as follows: (1) The shield plug does not form a seal with the tube vault wall, thus allowing the hydrogen gas to diffuse past the shield plug to the upper section of the tube vault. (2) The tube vault end-cap leaks sufficiently to allow air to be drawn into the tube vault by the off-gas system, thereby purging hydrogen from the upper section of the tube vault. (3) Any hydrogen gas generated completely mixes with the other gases present in the lower section of the tube vault and does not stratify beneath the shield plug. (4) The diffusion coefficient determined from the literature for constant diffusion of hydrogen in air is valid. The coefficient is corrected for temperatures from 0 to 25 C. Another assumption used in the model, that hydrogen generated by radiolytic decomposition of hydrogen-bearing materials (e.g., moisture and plastic) leaks from the cans under steady-state condition, as opposed to a sudden release resulting from rupture of the can(s), was beyond the scope of this investigation. Several parameters from the original

  20. A composite of borohydride and super absorbent polymer for hydrogen generation

    Science.gov (United States)

    Li, Z. P.; Liu, B. H.; Liu, F. F.; Xu, D.

    To develop a hydrogen source for underwater applications, a composite of sodium borohydride and super absorbent polymer (SAP) is prepared by ball milling sodium borohydride powder with SAP powder, and by dehydrating an alkaline borohydride gel. When sodium polyacrylate (NaPAA) is used as the SAP, the resulting composite exhibits a high rate of borohydride hydrolysis for hydrogen generation. A mechanism of hydrogen evolution from the NaBH 4-NaPAA composite is suggested based on structure analysis by X-ray diffraction and scanning electron microscopy. The effects of water and NiCl 2 content in the precursor solution on the hydrogen evolution behavior are investigated and discussed.

  1. HOGEN{trademark} proton exchange membrane hydrogen generators: Commercialization of PEM electrolyzers

    Energy Technology Data Exchange (ETDEWEB)

    Smith, W.F.; Molter, T.M. [Proton Energy Systems, Inc., Rocky Hill, CT (United States)

    1997-12-31

    PROTON Energy Systems` new HOGEN series hydrogen generators are Proton Exchange Membrane (PEM) based water electrolyzers designed to generate 300 to 1000 Standard Cubic Feet Per Hour (SCFH) of high purity hydrogen at pressures up to 400 psi without the use of mechanical compressors. This paper will describe technology evolution leading to the HOGEN, identify system design performance parameters and describe the physical packaging and interfaces of HOGEN systems. PEM electrolyzers have served US and UK Navy and NASA needs for many years in a variety of diverse programs including oxygen generators for life support applications. In the late 1970`s these systems were advocated for bulk hydrogen generation through a series of DOE sponsored program activities. During the military buildup of the 1980`s commercial deployment of PEM hydrogen generators was de-emphasized as priority was given to new Navy and NASA PEM electrolysis systems. PROTON Energy Systems was founded in 1996 with the primary corporate mission of commercializing PEM hydrogen generators. These systems are specifically designed and priced to meet the needs of commercial markets and produced through manufacturing processes tailored to these applications. The HOGEN series generators are the first step along the path to full commercial deployment of PEM electrolyzer products for both industrial and consumer uses. The 300/1000 series are sized to meet the needs of the industrial gases market today and provide a design base that can transition to serve the needs of a decentralized hydrogen infrastructure tomorrow.

  2. Next Generation Hydrogen Station Composite Data Products: Retail Stations, Data through Quarter 4 of 2016

    Energy Technology Data Exchange (ETDEWEB)

    Sprik, Sam [National Renewable Energy Lab. (NREL), Golden, CO (United States); Kurtz, Jennifer [National Renewable Energy Lab. (NREL), Golden, CO (United States); Ainscough, Chris [National Renewable Energy Lab. (NREL), Golden, CO (United States); Saur, Genevieve [National Renewable Energy Lab. (NREL), Golden, CO (United States); Peters, Michael [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2017-05-31

    This publication includes 86 composite data products (CDPs) produced for next generation hydrogen stations, with data through the fourth quarter of 2016. These CDPs include data from retail stations only.

  3. Embedded system based on PWM control of hydrogen generator with SEPIC converter

    Science.gov (United States)

    Fall, Cheikh; Setiawan, Eko; Habibi, Muhammad Afnan; Hodaka, Ichijo

    2017-09-01

    The objective of this paper is to design and to produce a micro electrical plant system based on fuel cell for teaching material-embedded systems in technical vocational training center. Based on this, the student can experience generating hydrogen by fuel cells, controlling the rate of hydrogen generation by the duty ration of single-ended primary-inductor converter(SEPIC), drawing the curve rate of hydrogen to duty ratio, generating electrical power by using hydrogen, and calculating the fuel cell efficiency when it is used as electrical energy generator. This project is of great importance insofar as students will need to acquire several skills to be able to realize it such as continuous DC DC conversion and the scientific concept behind the converter, the regulation of systems with integral proportional controllers, the installation of photovoltaic cells, the use of high-tech sensors, microcontroller programming, object-oriented programming, mastery of the fuel cell syste

  4. Next Generation Hydrogen Station Composite Data Products: Retail Stations, Data Through Quarter 3 of 2016

    Energy Technology Data Exchange (ETDEWEB)

    Sprik, Sam [National Renewable Energy Lab. (NREL), Golden, CO (United States); Kurtz, Jennifer [National Renewable Energy Lab. (NREL), Golden, CO (United States); Ainscough, Chris [National Renewable Energy Lab. (NREL), Golden, CO (United States); Saur, Genevieve [National Renewable Energy Lab. (NREL), Golden, CO (United States); Peters, Michael [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jeffers, Matthew [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2017-03-07

    This publication includes 80 composite data products (CDPs) produced in Spring 2016 for next generation hydrogen stations, with data through the third quarter of 2016. These CDPs include data from retail stations only.

  5. Workshop on Hydrogen Storage and Generation for Medium-Power and -Energy Applications

    National Research Council Canada - National Science Library

    Matthews, Michael

    1998-01-01

    This report summarizes the Workshop on Hydrogen Storage and Generation Technologies for Medium-Power and -Energy Applications which was held on April 8-10, 1997 at the Radisson Hotel Orlando Airport in Orlando, Florida...

  6. Next Generation Hydrogen Station Composite Data Products: Retail Stations, Data through Quarter 2 of 2017

    Energy Technology Data Exchange (ETDEWEB)

    Sprik, Samuel [National Renewable Energy Lab. (NREL), Golden, CO (United States); Kurtz, Jennifer M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Ainscough, Christopher D. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Saur, Genevieve [National Renewable Energy Lab. (NREL), Golden, CO (United States); Peters, Michael C. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2017-12-05

    This publication includes 92 composite data products (CDPs) produced for next generation hydrogen stations, with data through the second quarter of 2017. These CDPs include data from retail stations only.

  7. ENVIRONMENTAL TECHNOLOGY VERIFICATION REPORT: BIOQUELL, INC. CLARIS C HYDROGEN PEROXIDE GAS GENERATOR

    Science.gov (United States)

    The Environmental Technology Verification report discusses the technology and performance of the Clarus C Hydrogen Peroxide Gas Generator, a biological decontamination device manufactured by BIOQUELL, Inc. The unit was tested by evaluating its ability to decontaminate seven types...

  8. Cyanogel-derived N-doped C nanosheets immobilizing Pd-P nanoparticles: One-pot synthesis and enhanced hydrogenation catalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hao; Yan, Xiaohong; Huang, Yundi; Zhang, Mengru; Tang, Yawen; Sun, Dongmei; Xu, Lin, E-mail: njuxulin@gmail.com; Wei, Shaohua, E-mail: weishaohua@njnu.edu.cn

    2017-02-28

    Highlights: • Cyanogel-bridged approach was developed for the synthesis of Pd-P@N-Cnanosheets. • Pd-P@N-C nanosheets exhibit high activity and stability for reduction of 4-NP. • Compositional and structural advantages account for the high catalytic activity. • The feasible synthesis could be extendable to other carbon-based nanohybrids. - Abstract: For Pd-based nanocatalysts, stabilization of Pd nanoparticles on carbon support could not only effectively avoid particle aggregation and maintain catalytic stability during catalytic processes, but also facilitate enhancing the catalytic activity due to the synergy between Pd nanoparticles and carbon support. Furthermore, the incorporation of non-metal of phosphorus (P) into Pd could effectively modulate the electronic structure of Pd and thus help to boost the catalytic properties. However, one-pot synthesis of such nanohybrids remains a great challenge due to the distinct physiochemical properties of Pd, P and C components. Herein, we demonstrate a one-pot and scalable synthesis of highly dispersed PdP alloy nanoparticle-immobilized on N-doped graphitic carbon nanosheets (abbreviated as Pd-P@N-C nanosheets) by using inorganic-organic hybrid cyanogel as a reaction precursor. In virtue of both compositional and structural advantages, the as-synthesized Pd-P@N-C nanosheets manifest a superior catalytic activity and stability toward the hydrogenation of 4-nitrophenol (4-NP). We believe that the present work will provide a feasible and versatile strategy for the development of efficient catalysts for environmental remediation and can also be extendable to other carbon-based nanohybrids with desirable functionalities.

  9. Low-Cost High-Pressure Hydrogen Generator

    Energy Technology Data Exchange (ETDEWEB)

    Cropley, Cecelia C.; Norman, Timothy J.

    2008-04-02

    Electrolysis of water, particularly in conjunction with renewable energy sources, is potentially a cost-effective and environmentally friendly method of producing hydrogen at dispersed forecourt sites, such as automotive fueling stations. The primary feedstock for an electrolyzer is electricity, which could be produced by renewable sources such as wind or solar that do not produce carbon dioxide or other greenhouse gas emissions. However, state-of-the-art electrolyzer systems are not economically competitive for forecourt hydrogen production due to their high capital and operating costs, particularly the cost of the electricity used by the electrolyzer stack. In this project, Giner Electrochemical Systems, LLC (GES) developed a low cost, high efficiency proton-exchange membrane (PEM) electrolysis system for hydrogen production at moderate pressure (300 to 400 psig). The electrolyzer stack operates at differential pressure, with hydrogen produced at moderate pressure while oxygen is evolved at near-atmospheric pressure, reducing the cost of the water feed and oxygen handling subsystems. The project included basic research on catalysts and membranes to improve the efficiency of the electrolysis reaction as well as development of advanced materials and component fabrication methods to reduce the capital cost of the electrolyzer stack and system. The project culminated in delivery of a prototype electrolyzer module to the National Renewable Energy Laboratory for testing at the National Wind Technology Center. Electrolysis cell efficiency of 72% (based on the lower heating value of hydrogen) was demonstrated using an advanced high-strength membrane developed in this project. This membrane would enable the electrolyzer system to exceed the DOE 2012 efficiency target of 69%. GES significantly reduced the capital cost of a PEM electrolyzer stack through development of low cost components and fabrication methods, including a 60% reduction in stack parts count. Economic

  10. Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

    Science.gov (United States)

    Patki, Gauri Dilip

    Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per

  11. Influence of different preparation conditions on catalytic activity of ag /gama-al/sub 2/o/sub 3/ for hydrogenation of coal slime pyrolysis

    International Nuclear Information System (INIS)

    Lei, Z.; Rong, C.

    2014-01-01

    This paper, introducing variable conditional factors with Ag/AL/sub 2/O/sub 3/ as catalyst, selects five variables to investigate the influences of experimental conditions on Ag/Al2O/sub 3/ catalytic activity and define the optimal process conditions. These variables include Ag loading amount, calcinations temperature, calcinations time, reduction temperature, reduction time. X ray diffraction (XRD), hydrogen temperature-programmed reduction (TPR), X ray photoelectron spectrum (XPS) and scanning electron microscopy (SEM) were utilized to characterize the catalytic activity of Ag/-Al/sub 2/O/sub 3/, active center structure and state and those of carrier were emphatically studied, In the meantime the effects of active center and carrier on catalytic activity are studied. The results showed that: (1) In the range of 600 degree C-900 degree C, the catalytic activity of Ag/-Al/sub 2/O/sub 3/ with different loading showed little difference when changing loading amount, in the range of 900 degree C-1100 degree C, when the loading was 5%, the catalytic activity was very high; From the XRD and SEM characterizations, when the loading was 5%, it showed strong intensity diffraction peak of Ag crystal, crystal Ag is the most important activity center to promote hydrogen yield. (2) the catalytic activity of Ag/-Al/sub 2/O/sub 3/ at 450 degree C was considerably higher than that at 400 degree C and 500 degree C. By BET, XRD and SEM characterization, it can be seen, the diffraction peaks intensity of Ag crystal at 450 degree C is higher and sharper than that at 400 degree C and 500 degree C and with the increase of calcinations temperature, the specific surface area of catalysts also increased. (3) In the range of 600 degree C - 1000 degree C, the effects of calcinations time can be negligible, while, with temperature higher than 1000 degree C, 4-hour-calcinations-time catalyst exhibits a more noticeable catalytic activity than 3-hour and 5-hour catalyst do; From the XRD

  12. A comparative parametric study of a catalytic plate methane reformer coated with segmented and continuous layers of combustion catalyst for hydrogen production

    Science.gov (United States)

    Mundhwa, Mayur; Parmar, Rajesh D.; Thurgood, Christopher P.

    2017-03-01

    A parametric comparison study is carried out between segmented and conventional continuous layer configurations of the coated combustion-catalyst to investigate their influence on the performance of methane steam reforming (MSR) for hydrogen production in a catalytic plate reactor (CPR). MSR is simulated on one side of a thin plate over a continuous layer of nickel-alumina catalyst by implementing an experimentally validated surface microkinetic model. Required thermal energy for the MSR reaction is supplied by simulating catalytic methane combustion (CMC) on the opposite side of the plate over segmented and continuous layer of a platinum-alumina catalyst by implementing power law rate model. The simulation results of both coating configurations of the combustion-catalyst are compared using the following parameters: (1) co-flow and counter-flow modes between CMC and MSR, (2) gas hourly space velocity and (3) reforming-catalyst thickness. The study explains why CPR designed with the segmented combustion-catalyst and co-flow mode shows superior performance not only in terms of high hydrogen production but also in terms of minimizing the maximum reactor plate temperature and thermal hot-spots. The study shows that the segmented coating requires 7% to 8% less combustion-side feed flow and 70% less combustion-catalyst to produce the required flow of hydrogen (29.80 mol/h) on the reforming-side to feed a 1 kW fuel-cell compared to the conventional continuous coating of the combustion-catalyst.

  13. Effect of carrier nature and Pt concentration on catalytic properties of deposited catalysts with respect to reaction of homomolecular isotopic exchange of hydrogen

    International Nuclear Information System (INIS)

    Korabel'nikova, L.M.; Vasilevich, A.A.

    1987-01-01

    Effect of carrier (Al 2 O 3 and SiO 2 ) nature and Pt concentration in deposited catalysts with respect to reaction of homomolecular isotopic exchange (HMIE) of hydrogen at -196 deg C and 66,6 Pa (0.5 mm of mercury) is studied. Dependence of specific catalytic activity of Pt/Al 2 O 3 and Pt/SiO 2 on platinum concentration is shown. It is found that large platinum crystallites in Pt/SiO 2 system have higher activity than small ones. The carrier effect on catalytic and surface properties of deposited platinum is detected. The most noticeably the carrier effect is manifested in the ranges of small degrees of carrier surface filling with metal. Optimum platinum concentrations in Pt/Al 2 O 3 and Pt/SiO 2 catalysts for hyrogen HMIE reaction are determined

  14. Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H{sub 2} generation

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong, E-mail: zdnan@yzu.edu.cn

    2016-11-01

    Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H{sub 2} gas by hydrolysis of NaBH{sub 4} solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH{sub 4} was calculated to be about 15.42 kJ mol{sup −1}. The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H{sub 2} gas.

  15. Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H2 generation

    International Nuclear Information System (INIS)

    Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong

    2016-01-01

    Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H 2 gas by hydrolysis of NaBH 4 solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH 4 was calculated to be about 15.42 kJ mol −1 . The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H 2 gas.

  16. Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

    Science.gov (United States)

    Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

    2015-08-11

    Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

  17. Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

    Energy Technology Data Exchange (ETDEWEB)

    Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

    2017-12-19

    Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

  18. Near-Monodisperse Ni-Cu Bimetallic Nanocrystals of Variable Composition: Controlled Synthesis and Catalytic Activity for H2 Generation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yawen; Huang, Wenyu; Habas, Susan E.; Kuhn, John N.; Grass, Michael E.; Yamada, Yusuke; Yang, Peidong; Somorjai, Gabor A.

    2008-07-22

    Near-monodisperse Ni{sub 1-x}Cu{sub x} (x = 0.2-0.8) bimetallic nanocrystals were synthesized by a one-pot thermolysis approach in oleylamine/1-octadecene, using metal acetylacetonates as precursors. The nanocrystals form large-area 2D superlattices, and display a catalytic synergistic effect in the hydrolysis of NaBH{sub 4} to generate H{sub 2} at x = 0.5 in a strongly basic medium. The Ni{sub 0.5}Cu{sub 0.5} nanocrystals show the lowest activation energy, and also exhibit the highest H{sub 2} generation rate at 298 K.

  19. Process for recycling waste aluminum with generation of high-pressure hydrogen.

    Science.gov (United States)

    Hiraki, Takehito; Yamauchi, Satoru; Iida, Masayasu; Uesugi, Hiroshi; Akiyama, Tomohiro

    2007-06-15

    An innovative environmently friendly hydrolysis process for recycling waste aluminum with the generation of high-pressure hydrogen has been proposed and experimentally validated. The effect of the concentration of sodium hydroxide solution on hydrogen generation rate was the main focus of the study. In the experiments, distilled water and aluminum powder were placed in the pressure-resistance reactor made of Hastelloy, and was compressed to a desired constant water pressure using a liquid pump. The sodium hydroxide solution was supplied by liquid pump with different concentrations (from 1.0 to 5.0 mol/dm3) at a constant flow rate into the reactor by replacing the distilled water, and the rate of hydrogen generated was measured simultaneously. The liquid temperature in the reactor increased due to the exothermic reaction given by Al + OH(-) + 3H2O = 1.5H2 + Al(OH)4(-) + 415.6 kJ. Therefore, a high-pressure hydrogen was generated at room temperature by mixing waste aluminum and sodium hydroxide solution. As the hydrogen compressor used in this process consumes less energy than the conventional one, the generation of hydrogen having a pressure of almost 30 MPa was experimentally validated together with Al(OH)3, a useful byproduct.

  20. International Conference on Solar Concentrators for the Generation of Electricity or Hydrogen: Book of Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    McConnell, R.; Symko-Davies, M.; Hayden, H.

    2005-05-01

    The International Conference on Solar Concentrators for the Generation of Electricity or Hydrogen provides an opportunity to learn about current significant research on solar concentrators for generating electricity or hydrogen. The conference will emphasize in-depth technical discussions of recent achievements in technologies that convert concentrated solar radiation to electricity or hydrogen, with primary emphasis on photovoltaic (PV) technologies. Very high-efficiency solar cells--above 37%--were recently developed, and are now widely used for powering satellites. This development demands that we take a fresh look at the potential of solar concentrators for generating low-cost electricity or hydrogen. Solar electric concentrators could dramatically overtake other PV technologies in the electric utility marketplace because of the low capital cost of concentrator manufacturing facilities and the larger module size of concentrators. Concentrating solar energy also has advantages for th e solar generation of hydrogen. Around the world, researchers and engineers are developing solar concentrator technologies for entry into the electricity generation market and several have explored the use of concentrators for hydrogen production. The last conference on the subject of solar electric concentrators was held in November of 2003 and proved to be an important opportunity for researchers and developers to share new and crucial information that is helping to stimulate projects in their countries.

  1. Solvent dependent asymmetric hydrogenation with self-assembled catalysts: a combined catalytic, NMR- and IR-study.

    Science.gov (United States)

    Shuklov, Ivan A; Dubrovina, Natalia V; Barsch, Enrico; Ludwig, Ralf; Michalik, Dirk; Börner, Armin

    2009-03-28

    For the first time the hydrogen bond based structure of self-aggregated Rh-phosphine complexes in fluorinated alcohols was directly determined, which gives a rationale for the high enantioselectivity observed in the asymmetric hydrogenation.

  2. Catalytic activity of molybdenum carbide for hydrogen generation via diesel reforming

    Science.gov (United States)

    Cheekatamarla, Praveen K.; Thomson, William J.

    The activity of a bulk molybdenum carbide catalyst for the steam (SR) and oxidative-steam reforming (OSR) of hexadecane has been studied with and without the presence of aromatic coke precursors and sulfur compounds. It is shown that this catalyst can be stable under very low steam:carbon ratios at temperatures as low as 885 °C under OSR conditions, and 965 °C under SR conditions. Using benzo-thiophene as a model sulfur compound at concentrations as high as 500 ppmw, the degree of deactivation was found to be dependent on the sulfur concentration but was minimal at concentrations below 100 ppmw. Experiments confirmed that the sulfur poisoning is reversible and characterization studies suggested the formation of sulfur entities, which lead to carbide oxidation and subsequent coking. There was minimal effect of the aromatic species on the catalyst stability.

  3. Zircaloy-oxidation and hydrogen-generation rates in degraded-core accident situations

    International Nuclear Information System (INIS)

    Chung, H.M.; Thomas, G.R.

    1983-02-01

    Oxidation of Zircaloy cladding is the primary source of hydrogen generated during a degraded-core accident. In this paper, reported Zircaloy oxidation rates, either measured at 1500 to 1850 0 C or extrapolated from the low-temperature data obtained at 0 C, are critically reviewed with respect to their applicability to a degraded-core accident situation in which the high-temperature fuel cladding is likely to be exposed to and oxidized in mixtures of hydrogen and depleted steam, rather than in an unlimited flux of pure steam. New results of Zircaloy oxidation measurements in various mixtures of hydrogen and steam are reported for >1500 0 C. The results show significantly smaller oxidation and, hence, hydrogen-generation rates in the mixture, compared with those obtained in pure steam. It is also shown that a significant fraction of hydrogen, generated as a result of Zircaloy oxidation, is dissolved in the cladding material itself, which prevents that portion of hydrogen from reaching the containment building space. Implications of these findings are discussed in relation to a more realistic method of quantifying the hydrogen source term for a degraded-core accident analysis

  4. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Nørskov, Jens K.

    2015-01-01

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized...... evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates...

  5. Defects generation by hydrogen passivation of polycrystalline silicon thin films

    Czech Academy of Sciences Publication Activity Database

    Honda, Shinya; Mates, Tomáš; Ledinský, Martin; Fejfar, Antonín; Kočka, Jan; Yamazaki, T.; Uraoka, Y.; Fuyuki, T.; Boldyryeva, Hanna; Macková, Anna; Peřina, Vratislav

    2006-01-01

    Roč. 80, - (2006), s. 653-657 ISSN 0038-092X R&D Projects: GA MŽP(CZ) SM/300/1/03; GA MŽP(CZ) SN/3/172/05; GA AV ČR IAA1010413; GA ČR(CZ) GD202/05/H003; GA AV ČR IAA1010316 Institutional research plan: CEZ:AV0Z10100521; CEZ:AV0Z10480505 Keywords : hydrogen passivation * ERDA * photoluminescence * Raman spectroscopy * Si-H 2 bonding * H 2 molecules * grain size. Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.431, year: 2006

  6. Enzymatic generation of hydrogen peroxide shows promising antifouling effect

    DEFF Research Database (Denmark)

    Kristensen, J.B.; Olsen, Stefan Møller; Laursen, B.S.

    2010-01-01

    The antifouling (AF) potential of hydrogen peroxide (H2O2) produced enzymatically in a coating containing starch, glucoamylase, and hexose oxidase was evaluated in a series of laboratory tests and in-sea field trials. Dissolved H2O2 inhibited bacterial biofilm formation by eight of nine marine...... Proteobacteria, tested in microtiter plates. However, enzymatically produced H2O2 released from a coating did not impede biofilm formation by bacteria in natural seawater tested in a biofilm reactor. A field trial revealed a noticeable effect of the enzyme system: after immersion in the North Sea for 97 days...

  7. Technological forecasting applied to the processes of hydrogen generation; Previsao tecnologica sobre os processos de geracao de hidrogenio

    Energy Technology Data Exchange (ETDEWEB)

    Nakano, Milton Satocy; Oliveira, Wagner dos Santos [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)], e-mails: msnakano@usp.br; wagner@ipen.br

    2008-11-15

    Fuel cells are attracting interest as efficient and clean energy conversion devices. Hydrogen is the combustible of the fuel cells and must be generated by an efficient and clean method. This work exploits Delphi methodology of technological forecasting applied to hydrogen generation and identifies the most probable methods that, in future, can be used to obtain hydrogen in Brazil. (author)

  8. Catalytic Hydrogenation of the Sweet Principles of Stevia rebaudiana, Rebaudioside B, Rebaudioside C, and Rebaudioside D and Sensory Evaluation of Their Reduced Derivatives

    Science.gov (United States)

    Prakash, Indra; Campbell, Mary; Chaturvedula, Venkata Sai Prakash

    2012-01-01

    Catalytic hydrogenation of rebaudioside B, rebaudioside C, and rebaudioside D; the three ent-kaurane diterpene glycosides isolated from Stevia rebaudiana was carried out using Pd(OH)2. Reduction of steviol glycosides was performed using straightforward synthetic chemistry with the catalyst Pd(OH)2 and structures of the corresponding dihydro derivatives were characterized on the basis of 1D and 2D nuclear magnetic resonance (NMR) spectral data indicating that all are novel compounds being reported for the first time. Also, the taste properties of all reduced compounds were evaluated against their corresponding original steviol glycosides and sucrose. PMID:23203115

  9. Isotactic and Syndiotactic Alternating Ethylene/Propylene Copolymers Obtained Through Non-Catalytic Hydrogenation of Highly Stereoregular cis-1,4 Poly(1,3-diene)s.

    Science.gov (United States)

    Ricci, Giovanni; Boccia, Antonella Caterina; Leone, Giuseppe; Pierro, Ivana; Zanchin, Giorgia; Scoti, Miriam; Auriemma, Finizia; De Rosa, Claudio

    2017-05-06

    The homogeneous non-catalytic hydrogenation of cis -1,4 poly(isoprene), isotactic cis -1,4 poly(1,3-pentadiene) and syndiotactic cis -1,4 poly(1,3-pentadiene) with diimide, formed by thermal decomposition of para -toluenesulfonylhydrazide, is examined. Perfectly alternating ethylene/propylene copolymers having different tacticity (i.e., isotactic and syndiotactic), which are difficult to synthesize by stereospecific copolymerization of the corresponding monomers, are obtained. Both isotactic and syndiotactic alternating ethylene/propylene copolymers are amorphous, with very low glass transition temperatures.

  10. Catalytic Hydrogenation of the Sweet Principles of Stevia rebaudiana, Rebaudioside B, Rebaudioside C, and Rebaudioside D and Sensory Evaluation of Their Reduced Derivatives

    Directory of Open Access Journals (Sweden)

    Mary Campbell

    2012-11-01

    Full Text Available Catalytic hydrogenation of rebaudioside B, rebaudioside C, and rebaudioside D; the three ent-kaurane diterpene glycosides isolated from Stevia rebaudiana was carried out using Pd(OH2. Reduction of steviol glycosides was performed using straightforward synthetic chemistry with the catalyst Pd(OH2 and structures of the corresponding dihydro derivatives were characterized on the basis of 1D and 2D nuclear magnetic resonance (NMR spectral data indicating that all are novel compounds being reported for the first time. Also, the taste properties of all reduced compounds were evaluated against their corresponding original steviol glycosides and sucrose.

  11. Electrodeposited synthesis of self-supported Ni-P cathode for efficient electrocatalytic hydrogen generation

    Directory of Open Access Journals (Sweden)

    Ruixian Wu

    2016-06-01

    Full Text Available One of the key challenges for electrochemical water splitting is the development of low-cost and efficient hydrogen evolution cathode. In this work, a self-supported Ni-P cathode was synthesized by a facile electrodeposition method. The composition and morphology were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The Ni-P cathode performed low onset over-potential, good catalytic activity and long-term stability under neutral and alkaline conditions. The mechanism of Ni-P electrode for hydrogen production was discussed by electrochemical impedance spectroscopy. The excellent performance of Ni-P cathode was mainly attributed to the synergistic effect of phosphate anions and the self-supported feature.

  12. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni{sub 2}P supported on active carbon

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yanli [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Sang, Huanxin [Tianjin Academy of Environmental Sciences, Tianjin 300191 (China); Wang, Kang [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Wang, Xitao, E-mail: wangxt@tju.edu.cn [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2014-10-15

    Graphical abstract: - Highlights: • Ni{sub 2}P catalyst is tested in dehydrogenation of isobutane for the first time. • The effects of Cs promoter on catalytic performance of Ni2P/AC were investigated. • Cs-Ni2P/AC exhibits high activity and selectivity for isobutane dehydrogenation. - Abstract: In this article, an environmentally friendly non-noble-metal class of Cs-Ni{sub 2}P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H{sub 2}-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni{sub 2}P particles, which decreases the strength of Ni-C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni{sub 2}P/AC catalysts display much higher catalytic performance as compared to Ni{sub 2}P/AC catalyst. Cs-Ni{sub 2}P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni{sub 2}P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

  13. Performance and Economics of Catalytic Glow Plugs and Shields in Direct Injection Natural Gas Engines for the Next Generation Natural Gas Vehicle Program: Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Mello, J. P.; Bezaire, D.; Sriramulu, S.; Weber, R.

    2003-08-01

    Subcontractor report details work done by TIAX and Westport to test and perform cost analysis for catalytic glow plugs and shields for direct-injection natural gas engines for the Next Generation Natural Gas Vehicle Program.

  14. High Surface Area Tungsten Carbides: Synthesis, Characterization and Catalytic Activity towards the Hydrogen Evolution Reaction in Phosphoric Acid at Elevated Temperatures

    DEFF Research Database (Denmark)

    Tomás García, Antonio Luis; Li, Qingfeng; Jensen, Jens Oluf

    2014-01-01

    Tungsten carbide powders were synthesized as a potential electrocatalyst for the hydrogen evolution reaction in phosphoric acid at elevated temperatures. With ammonium metatungstate as the precursor, two synthetic routes with and without carbon templates were investigated. Through the intermediate...... nitride route and with carbon black as template, the obtained tungsten carbide samples had higher BET area. In 100% H3PO4 at temperatures up to 185°C, the carbide powders showed superior activity towards the hydrogen evolution reaction. A deviation was found in the correlation between the BET area...... and catalytic activity; this was attributed to the presence of excess amorphous carbon in the carbide powder. TEM imaging and TGA-DTA results revealed a better correlation of the activity with the carbide particle size....

  15. CHALLENGES IN GENERATING HYDROGEN BY HIGH TEMPERATURE ELECTROLYSIS USING SOLID OXIDE CELLS

    Energy Technology Data Exchange (ETDEWEB)

    M. S. Sohal; J. E. O' Brien; C. M. Stoots; M. G. McKellar; J. S. Herring; E. A. Harvego

    2008-03-01

    Idaho National Laboratory’s (INL) high temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells is presented in this paper. The research results reported here have been obtained in a laboratory-scale apparatus. These results and common scale-up issues also indicate that for the technology to be successful in a large industrial setting, several technical, economical, and manufacturing issues have to be resolved. Some of the issues related to solid oxide cells are stack design and performance optimization, identification and evaluation of cell performance degradation parameters and processes, integrity and reliability of the solid oxide electrolysis (SOEC) stacks, life-time prediction and extension of the SOEC stack, and cost reduction and economic manufacturing of the SOEC stacks. Besides the solid oxide cells, balance of the hydrogen generating plant also needs significant development. These issues are process and ohmic heat source needed for maintaining the reaction temperature (~830°C), high temperature heat exchangers and recuperators, equal distribution of the reactants into each cell, system analysis of hydrogen and associated energy generating plant, and cost optimization. An economic analysis of this plant was performed using the standardized H2A Analysis Methodology developed by the Department of Energy (DOE) Hydrogen Program, and using realistic financial and cost estimating assumptions. The results of the economic analysis demonstrated that the HTE hydrogen production plant driven by a high-temperature helium-cooled nuclear power plant can deliver hydrogen at a cost of $3.23/kg of hydrogen assuming an internal rate of return of 10%. These issues need interdisciplinary research effort of federal laboratories, solid oxide cell manufacturers, hydrogen consumers, and other such stakeholders. This paper discusses research and development accomplished by INL on such issues and highlights associated challenges that need to

  16. Empirical rate equation model and rate calculations of hydrogen generation for Hanford tank waste

    International Nuclear Information System (INIS)

    HU, T.A.

    1999-01-01

    Empirical rate equations are derived to estimate hydrogen generation based on chemical reactions, radiolysis of water and organic compounds, and corrosion processes. A comparison of the generation rates observed in the field with the rates calculated for twenty eight tanks shows agreement within a factor of two to three

  17. Hydrogen Fuel Cell Analysis: Lessons Learned from Stationary Power Generation Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Scott E. Grasman; John W. Sheffield; Fatih Dogan; Sunggyu Lee; Umit O. Koylu; Angie Rolufs

    2010-04-30

    This study considered opportunities for hydrogen in stationary applications in order to make recommendations related to RD&D strategies that incorporate lessons learned and best practices from relevant national and international stationary power efforts, as well as cost and environmental modeling of pathways. The study analyzed the different strategies utilized in power generation systems and identified the different challenges and opportunities for producing and using hydrogen as an energy carrier. Specific objectives included both a synopsis/critical analysis of lessons learned from previous stationary power programs and recommendations for a strategy for hydrogen infrastructure deployment. This strategy incorporates all hydrogen pathways and a combination of distributed power generating stations, and provides an overview of stationary power markets, benefits of hydrogen-based stationary power systems, and competitive and technological challenges. The motivation for this project was to identify the lessons learned from prior stationary power programs, including the most significant obstacles, how these obstacles have been approached, outcomes of the programs, and how this information can be used by the Hydrogen, Fuel Cells & Infrastructure Technologies Program to meet program objectives primarily related to hydrogen pathway technologies (production, storage, and delivery) and implementation of fuel cell technologies for distributed stationary power. In addition, the lessons learned address environmental and safety concerns, including codes and standards, and education of key stakeholders.

  18. Direct steam reforming of diesel and diesel–biodiesel blends for distributed hydrogen generation

    OpenAIRE

    Martin, Stefan; Kraaij, Gerard; Ascher, Torsten; Baltzopoulou, Penelope; Karagiannakis, George; Wails, David; Wörner, Antje

    2015-01-01

    Distributed hydrogen generation from liquid fuels has attracted increasing attention in the past years. Petroleum-derived fuels with already existing infrastructure benefit from high volumetric and gravimetric energy densities, making them an interesting option for cost competitive decentralized hydrogen production. In the present study, direct steam reforming of diesel and diesel blends (7 vol.% biodiesel) is investigated at various operating conditions using a proprietary precious metal ...

  19. Lessons learned from hydrogen generation and burning during the TMI-2 event

    International Nuclear Information System (INIS)

    Henrie, J.O.; Postma, A.K.

    1987-05-01

    This document summarizes what has been learned from generation of hydrogen in the reactor core and the hydrogen burn that occurred in the containment building of the Three Mile Island Unit No. 2 (TMI-2) nuclear power plant on March 28, 1979. During the TMI-2 loss-of-coolant accident (LOCA), a large quantity of hydrogen was generated by a zirconium-water reaction. The hydrogen burn that occurred 9 h and 50 min after the initiation of the TMI-2 accident went essentially unnoticed for the first few days. Even through the burn increased the containment gas temperature and pressure to 1200 0 F (650 0 C) and 29 lb/in 2 (200 kPa) gage, there was no serious threat to the containment building. The processes, rates, and quantities of hydrogen gas generated and removed during and following the LOCA are described in this report. In addition, the methods which were used to define the conditions that existed in the containment building before, during, and after the hydrogen burn are described. The results of data evaluations and engineering calculations are presented to show the pressure and temperature histories of the atmosphere in various containment segments during and after the burn. Material and equipment in reactor containment buildings can be protected from burn damage by the use of relatively simple enclosures or insulation

  20. Agro-industrial waste-mediated synthesis and characterization of gold and silver nanoparticles and their catalytic activity for 4-nitroaniline hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Dauthal, Preeti; Mukhopadhyay, Mausumi [S.V. National Institute of Technology, Surat (India)

    2015-05-15

    The biosynthesis of gold (Au-NPs) and silver nanoparticles (Ag-NPs) using agro-industrial waste Citrus aurantifolia peel extract as a bio-reducing agent is reported. Catalytic activity of nanoparticles (NPs) was evaluated for hydrogenation of anthropogenic pollutant 4-nitroaniline (4-NA). Both synthesized NPs were nearly spherical and distributed in size range of 6-46 and 10-32 nm for Au-NPs and Ag-NPs, respectively. XRD analysis revealed face centered cubic (fcc) structure of both NPs. ζ potential value obtained from colloidal solution of Au-NPs and Ag-NPs was −28.0 and −26.1mV, respectively, indicating the stability of the NPs in colloidal solution. FTIR spectra supported the role of citric and ascorbic acids of peel extract for biosynthesis and stabilization of NPs. The biosynthesized NPs exhibited excellent catalytic activity for hydrogenation of 4-NA in the presence of NaBH{sub 4}.

  1. High Performance, Low Cost Hydrogen Generation from Renewable Energy

    Energy Technology Data Exchange (ETDEWEB)

    Ayers, Katherine [Proton OnSite; Dalton, Luke [Proton OnSite; Roemer, Andy [Proton OnSite; Carter, Blake [Proton OnSite; Niedzwiecki, Mike [Proton OnSite; Manco, Judith [Proton OnSite; Anderson, Everett [Proton OnSite; Capuano, Chris [Proton OnSite; Wang, Chao-Yang [Penn State University; Zhao, Wei [Penn State University

    2014-02-05

    Renewable hydrogen from proton exchange membrane (PEM) electrolysis is gaining strong interest in Europe, especially in Germany where wind penetration is already at critical levels for grid stability. For this application as well as biogas conversion and vehicle fueling, megawatt (MW) scale electrolysis is required. Proton has established a technology roadmap to achieve the necessary cost reductions and manufacturing scale up to maintain U.S. competitiveness in these markets. This project represents a highly successful example of the potential for cost reduction in PEM electrolysis, and provides the initial stack design and manufacturing development for Proton’s MW scale product launch. The majority of the program focused on the bipolar assembly, from electrochemical modeling to subscale stack development through prototyping and manufacturing qualification for a large active area cell platform. Feasibility for an advanced membrane electrode assembly (MEA) with 50% reduction in catalyst loading was also demonstrated. Based on the progress in this program and other parallel efforts, H2A analysis shows the status of PEM electrolysis technology dropping below $3.50/kg production costs, exceeding the 2015 target.

  2. Hydrogen production from cheese whey by catalytic steam reforming: Preliminary study using lactose as a model compound

    International Nuclear Information System (INIS)

    Remón, J.; Laseca, M.; García, L.; Arauzo, J.

    2016-01-01

    Highlights: • Steam reforming of lactose: a promising strategy for cheese whey management. • Thermodynamic and experimental analyses of the effect of the operating conditions. • Reaction pathway showing the formation of the most important gas and liquid products. • Technical/energetic assessment: H 2 rich gas, C-free liquid and neutral energy process. - Abstract: Cheese whey is a yellowish liquid by-product of the cheese making process. Owing to its high BOD and COD values, this feedstock should not be directly discharged into the environment without appropriate treatment. Before dealing with real cheese whey, this work addresses the production of a rich hydrogen gas from lactose (the largest organic constituent of this waste) by catalytic steam reforming. This reforming process has been theoretically and experimentally studied. The theoretical study examines the effect of the temperature (300–600 °C), lactose concentration (1–10 wt.%) and N 2 (0–80 cm 3 STP/min) and liquid flow (0.1–0.5 mL/min) rates on the thermodynamic composition of the gas. The results show that the temperature and lactose concentration exerted the greatest influence on the thermodynamics. The experimental study, conducted in a fixed bed reactor using a Ni-based catalyst, considers the effect of the temperature (300–600 °C), lactose concentration (1–10 wt.%) and spatial time (4–16 g catalyst min/g lactose) on the global lactose conversion, product distribution on a carbon basis (gas, liquid and solid) and the compositions of the gas and liquid phases. Complete lactose conversion was achieved under all the experimental conditions. The carbon converted into gas, liquid and solid was 2–97%, 0–66% and 0–94%, respectively. The gas phase was made up of a mixture of H 2 (0–70 vol.%), CO 2 (20–70 vol.%), CO (2–34 vol.%) and CH 4 (0–3 vol.%). The liquid phase consisted of a mixture of aldehydes, ketones, carboxylic acids, sugars, furans, alcohols and phenols

  3. Dye-Sensitized Photocatalytic Water Splitting and Sacrificial Hydrogen Generation: Current Status and Future Prospects

    Directory of Open Access Journals (Sweden)

    Pankaj Chowdhury

    2017-05-01

    Full Text Available Today, global warming and green energy are important topics of discussion for every intellectual gathering all over the world. The only sustainable solution to these problems is the use of solar energy and storing it as hydrogen fuel. Photocatalytic and photo-electrochemical water splitting and sacrificial hydrogen generation show a promise for future energy generation from renewable water and sunlight. This article mainly reviews the current research progress on photocatalytic and photo-electrochemical systems focusing on dye-sensitized overall water splitting and sacrificial hydrogen generation. An overview of significant parameters including dyes, sacrificial agents, modified photocatalysts and co-catalysts are provided. Also, the significance of statistical analysis as an effective tool for a systematic investigation of the effects of different factors and their interactions are explained. Finally, different photocatalytic reactor configurations that are currently in use for water splitting application in laboratory and large scale are discussed.

  4. Hydrogen-oxygen steam generator applications for increasing the efficiency, maneuverability and reliability of power production

    Science.gov (United States)

    Schastlivtsev, A. I.; Borzenko, V. I.

    2017-11-01

    The comparative feasibility study of the energy storage technologies showed good applicability of hydrogen-oxygen steam generators (HOSG) based energy storage systems with large-scale hydrogen production. The developed scheme solutions for the use of HOSGs for thermal power (TPP) and nuclear power plants (NPP), and the feasibility analysis that have been carried out have shown that their use makes it possible to increase the maneuverability of steam turbines and provide backup power supply in the event of failure of the main steam generating equipment. The main design solutions for the integration of hydrogen-oxygen steam generators into the main power equipment of TPPs and NPPs, as well as their optimal operation modes, are considered.

  5. Utilization of hydrogen gas production for electricity generation in ...

    African Journals Online (AJOL)

    Lecturer

    2012-05-03

    % total sugar concentration of sugar ... 107 cfu/ml, pH was nearly constant at 6.0, and finally the H2 was drifted to fuel cell to generate electrical power until 4 V ..... hybrid system, reverse micelles and by metabolic engi- neering.

  6. Electrochemical catalytic reforming of oxygenated-organic compounds: a highly efficient method for production of hydrogen from bio-oil.

    Science.gov (United States)

    Yuan, Lixia; Chen, Yaqiong; Song, Chongfu; Ye, Tongqi; Guo, Qingxiang; Zhu, Qingshi; Torimoto, Youshifumi; Li, Quanxin

    2008-11-07

    A novel approach to produce hydrogen from bio-oil was obtained with high carbon conversion (>90%) and hydrogen yield (>90%) at Tcatalytic reforming of oxygenated-organic compounds over 18%NiO/Al(2)O(3) reforming catalyst; thermal electrons play important promoting roles in the decomposition and reforming of the oxygenated-organic compounds in the bio-oil.

  7. Chemical Plant Accidents in a Nuclear Hydrogen Generation Scheme

    International Nuclear Information System (INIS)

    Brown, Nicholas R.; Revankar, Shripad T.

    2011-01-01

    A high temperature nuclear reactor (HTR) could be used to drive a steam reformation plant, a coal gasification facility, an electrolysis plant, or a thermochemical hydrogen production cycle. Most thermochemical cycles are purely thermodynamic, and thus achieve high thermodynamic efficiency. HTRs produce large amounts of heat at high temperature (1100 K). Helium-cooled HTRs have many passive, or inherent, safety characteristics. This inherent safety is due to the high design basis limit of the maximum fuel temperature. Due to the severity of a potential release, containment of fission products is the single most important safety issue in any nuclear reactor facility. A HTR coupled to a chemical plant presents a complex system, due primarily to the interactive nature of both plants. Since the chemical plant acts as the heat sink for the nuclear reactor, it important to understand the interaction and feedback between the two systems. Process heat plants and HTRs are generally very different. Some of the major differences include: time constants of plants, safety standards, failure probability, and transient response. While both the chemical plant and the HTR are at advanced stages of testing individually, no serious effort has been made to understand the operation of the integrated system, especially during accident events that are initiated in the chemical plant. There is a significant lack of knowledge base regarding scaling and system integration for large scale process heat plants coupled to HTRs. Consideration of feedback between the two plants during time-dependent scenarios is absent from literature. Additionally, no conceptual studies of the accidents that could occur in either plant and impact the entire coupled system are present in literature

  8. Experimental and numerical investigation of the catalytic partial oxidation of methane to synthesis gas for power generation applications[Dissertation 17183

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, A.

    2007-07-01

    The present work addresses the catalytic partial oxidation (CPO) of methane to synthesis gas, with particular emphasis on power generation applications. A combined experimental and numerical investigation of methane partial oxidation to synthesis gas (H{sub 2}, CO) over rhodium-based catalysts has been carried out at pressures of up to 10 bar. The reactivity of the produced hydrogen and the suitably-low light-off temperatures of the CPO reactor, greatly facilitate operation of power generation gas turbines with reduced NO{sub x} emissions, stable operation with low calorific value fuels, and new combustion strategies for efficient CO{sub 2} capture. Those strategies utilize CPO of methane with oxygen (separated from air) and large exhaust gas recycle (H{sub 2}O and CO{sub 2}). An optically accessible catalytic channel-flow reactor was used to carry out Raman spectroscopy of major gas-phase species and laser induced fluorescence (LIF) of formaldehyde, in order to gain fundamental information on the catalytic and gas-phase chemical pathways. Transverse concentration profiles measured by the spontaneous Raman scattering technique determined the catalytic reactivity, while the LIF provided flame shapes and anchoring positions that, in turn, characterized the gaseous reactivity. Comparison between measurements and 2-D CFD computations, led to the validation of detailed catalytic and gas-phase reaction mechanisms. Experiments in a subscale gas-turbine honeycomb catalytic reactor have shown that the foregoing reaction mechanisms were also appropriate under gas-turbine relevant conditions with short reactant residence times. The light-off behavior of the subscale honeycomb reactor was reproduced by transient 2-D CFD computations. Ignition and extinction in CPO was studied. It was shown that, despite the chemical impact of the H{sub 2}O diluent during the transient catalytic ignition event, the light-off times themselves were largely unaffected by the exhaust gas dilution

  9. Performance of new generation TWC catalytic systems working under different conditions in order to reduce the emission of a global warming gas: N{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Mac-Beath, I.; Castillo, S.; Camposeco, R.; Moran-Pineda, M. [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico). Programa de Ingenieria Molecular

    2010-07-01

    In this work, three-way catalytic systems (TWC-K, TWC-M and TWC-P) were prepared and tested experimentally in order to analyze N{sub 2}O emissions. Various types and quantities of precious metals (Pt-Pd-Rh), and different mixed oxides (CexBayLazMgwO{sub 2}-Al{sub 2}O{sub 3}) to prepare the supports were used. The catalytic tests were carried out by using common exhaust gases from a gasoline engine under different oxidizing conditions. The TWC catalytic compositions were based on catalytic converters used in retrofitting programs in the Metropolitan Area in Mexico City. Fresh and aged TWC catalytic samples were tested; in both conditions, the catalytic compositions were characterized by BET, TEM-EDS and XRD in order to analyze the efficiency of the catalytic behavior. Due to the fact that the 4{sup th} TWC generation (Pd-Only TWC) has Pd as main active metal, the tested TWC catalytic samples were synthesized by having Pd in a higher proportion with regard to Pt and Rh used as complements with some differences in support composition. (orig.)

  10. Zircaloy oxidation and hydrogen generation behavior during severe accidents

    International Nuclear Information System (INIS)

    Cronenberg, A.W.; Miller, R.W.; Osetek, D.J.

    1987-01-01

    Zircaloy oxidation and H 2 generation data are presented for recent in-pile severe fuel damage tests. The principal questions investigated concern zircaloy melting and bundle reconfiguration effects on oxidation behavior. A comparison of H 2 generation and cladding temperature data indicate that significant oxidation occurred after the onset of fuel liquefaction. Posttest metallographic observations of the test debris also indicate a high degree of oxidation of once-molten zircaloy. Analysis of bundle reconfiguration effects indicate that essentially complete flow area blockage (>98%) would be required to retard steam flow through the degraded bundle so as to diminish H 2 production. Such extreme blockage conditions are not supported by posttest bundle examination

  11. Sodium borohydride hydrogen generator using Co–P/Ni foam catalysts for 200 W proton exchange membrane fuel cell system

    International Nuclear Information System (INIS)

    Oh, Taek Hyun; Gang, Byeong Gyu; Kim, Hyuntak; Kwon, Sejin

    2015-01-01

    The response characteristics of electroless-deposited Co–P/Ni foam catalysts for sodium borohydride hydrolysis were investigated. The effect of nickel foam geometry on the properties of the catalysts was evaluated. As the PPI (pores per inch) of the nickel foam increased, the hydrogen generation rate per gram of the deposited catalyst increased due to an increase in surface area. The response characteristics of various catalysts were compared under real operating conditions. When a thin nickel foam with high PPI was used, the response characteristics of the catalyst improved due to an increase in the amount of the deposited catalyst and surface area. Finally, a 200 W PEMFC (proton exchange membrane fuel cell) system using electroless-deposited Co–P/Ni foam (110 PPI) catalyst was investigated. The response time to reach a hydrogen generation rate sufficient for a 200 W PEMFC was 71 s, and the energy density of a 200 W fuel cell system for producing 600 Wh was 252.1 Wh/kg. A fuel cell system using Co–P/Ni foam catalysts can be widely used as a power source for mobile applications due to fast response characteristics and high energy density. - Highlights: • Response characteristics of Co–P/Ni foam catalysts are investigated. • Catalytic activity is improved with increase in PPI (pores per inch) of Ni foam. • Co–P/Ni foam (110 PPI) catalyst has improved response characteristics. • The energy density of a 200 W PEMFC system for producing 600 Wh is 252.1 Wh/kg. • Co–P/Ni foam (110 PPI) catalyst is suitable for fuel cell system.

  12. A reforming system for co-generation of hydrogen and mechanical work from methanol

    Science.gov (United States)

    Lyubovsky, Maxim; Walsh, Dennis

    The paper describes a reforming system for converting methanol into pure hydrogen. The system is based on an autothermal reforming reactor operating at elevated pressures followed by membrane-based hydrogen separation. The high-pressure membrane retentate stream is combusted and expanded through a turbine generating additional power. Process simulation illustrates the effects of the system operating parameters on performance and demonstrates system reforming efficiency up to ∼90%. When coupled with a PEM fuel cell and an electrical generator, overall fuel to electricity efficiency can be >48% depending upon the efficiency of a PEM fuel cell stack.

  13. Reforming system for co-generation of hydrogen and mechanical work

    Science.gov (United States)

    Lyubovsky, Maxim; Walsh, Dennis

    The paper describes a new design for a reforming system for converting hydrocarbon fuels into pure hydrogen. The system is based on an autothermal reforming (ATR) reactor operating at elevated pressures followed by membrane-based hydrogen separation. The high-pressure membrane discharge stream is combusted and expanded through a turbine generating additional power. Process simulation modeling illustrates the effect of pressure and other operating parameters on system performance and demonstrates a system reforming efficiency approaching 80%. When coupled with a PEM fuel cell and an electrical generator, fuel to electricity efficiency is above 40%. Other anticipated benefits of the system include compact size, simplicity in control and fast start up.

  14. Predicting efficiency of solar powered hydrogen generation using photovoltaic-electrolysis devices

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, Thomas L.; Kelly, Nelson A. [General Motors Research and Development Center, Chemical Science and Material Systems Laboratory, Mail Code 480-106-269, 30500 Mound Road, Warren, MI 48090-9055 (United States)

    2010-02-15

    Hydrogen fuel for fuel cell vehicles can be produced by using solar electric energy from photovoltaic (PV) modules for the electrolysis of water without emitting carbon dioxide or requiring fossil fuels. In the past, this renewable means of hydrogen production has suffered from low efficiency (2-6%), which increased the area of the PV array required and therefore, the cost of generating hydrogen. A comprehensive mathematical model was developed that can predict the efficiency of a PV-electrolyzer combination based on operating parameters including voltage, current, temperature, and gas output pressure. This model has been used to design optimized PV-electrolyzer systems with maximum solar energy to hydrogen efficiency. In this research, the electrical efficiency of the PV-electrolysis system was increased by matching the maximum power output and voltage of the photovoltaics to the operating voltage of a proton exchange membrane (PEM) electrolyzer, and optimizing the effects of electrolyzer operating current, and temperature. The operating temperature of the PV modules was also an important factor studied in this research to increase efficiency. The optimized PV-electrolysis system increased the hydrogen generation efficiency to 12.4% for a solar powered PV-PEM electrolyzer that could supply enough hydrogen to operate a fuel cell vehicle. (author)

  15. Hydrogen Generation in Microbial Reverse-Electrodialysis Electrolysis Cells Using a Heat-Regenerated Salt Solution

    KAUST Repository

    Nam, Joo-Youn

    2012-05-01

    Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m3 H2/m3·d, with a hydrogen yield of 3.4 mol H2/mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co- or counter-current) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes. © 2012 American Chemical Society.

  16. Catalytic Layer Optimization for Hydrogen Permeation Membranes Based on La5.5WO11.25-δ/La0.87Sr0.13CrO3-δComposites.

    Science.gov (United States)

    Escolástico, Sonia; Solı S, Cecilia; Kjølseth, Christian; Serra, Jose Manuel

    2017-10-18

    (LWO/LSC) composite is one of the most promising mixed ionic-electronic conducting materials for hydrogen separation at high temperature. However, these materials present limited catalytic surface activity toward H 2 activation and water splitting, which determines the overall H 2 separation rate. For the implementation of these materials as catalytic membrane reactors, effective catalytic layers have to be developed that are compatible and stable under the reaction conditions. This contribution presents the development of catalytic layers based on sputtered metals (Cu and Pd), electrochemical characterization by impendace spectroscopy, and the study of the H 2 flow obtained by coating them on 60/40-LWO/LSC membranes. Stability of the catalytic layers is also evaluated under H 2 permeation conditions and CH 4 -containing atmospheres.

  17. The analysis of mixtures of ortho and para-hydrogen and the catalytic conversion o.H2 → p.H2

    International Nuclear Information System (INIS)

    Botter, F.; Dirian, G.

    1956-01-01

    This report describes experiments undertaken to measure the catalytic activity at - 195 deg. C of different types of absorbents for the heterogeneous conversion o.H 2 → p.H 2 . The analytical method employed is a differential measurement of the thermal conductivity of the gas. In contrast to the classic method of FARKAS we have worked at room temperature (the difference of several per cent between the thermal conductivities of ortho and para-hydrogen at this temperature being found sufficiently great) and with a continuously recording system. The gas is at atmospheric pressure. We have investigated also the possibilities of an industrial katharometer which would allow a great extension to be given to this method of analysis. The instrument proved satisfactory. It has been checked that the paramagnetic conversion obeys first order kinetics. A certain number of absorbing substances were tested and amongst them, the active carbons, often used in the laboratory for the production of para-hydrogen, were shown to be the least active. A chromium oxide-aluminium oxide catalyst prepared from data available in the literature had a very great activity. In addition, some observations of the influence of adsorbed gases on the catalytic activity are reported: the comparison with the literature data is not easy due to the uncertainty in the physico-chemical nature of the absorbents used in the two cases. Finally, some bibliographic data relative to the properties of the two forms of hydrogen, their measurement, and the different mechanisms of interconversion are given. (author) [fr

  18. Coupling a PEM fuel cell and the hydrogen generation from aluminum waste cans

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Susana Silva; Albanil Sanchez, Loyda; Alvarez Gallegos, Alberto A. [Centro de Investigacion en Ingenieria y Ciencias Aplicadas, Av. Universidad 1001, Col. Chamilpa, Cuernavaca, Mor. CP 62210 (Mexico); Sebastian, P.J. [Centro de Investigacion en Energia-UNAM, 62580 Temixco, Morelos (Mexico); Cuerpo Academico de Energia y Sustentabilidad, UPCH, Tuxtla Gutierrez, Chiapas (Mexico)

    2007-10-15

    High purity hydrogen was generated from the chemical reaction of aluminum and sodium hydroxide. The aluminum used in this study was obtained from empty soft drink cans and treated with concentrated sulfuric acid to remove the paint and plastic film. One gram of aluminum was reacted with a solution of 2moldm{sup -3} of sodium hydroxide to produce hydrogen. The hydrogen produced from aluminum cans and oxygen obtained from a proton exchange membrane electrolyzer or air, was fed to a proton exchange membrane (PEM) fuel cell to produce electricity. Yields of 44 mmol of hydrogen contained in a volume of 1.760dm{sup 3} were produced from one gram of aluminum in a time period of 20 min. (author)

  19. Effect of torrefaction pretreatment and catalytic pyrolysis on the pyrolysis poly-generation of pine wood.

    Science.gov (United States)

    Chen, Dengyu; Li, Yanjun; Deng, Minsi; Wang, Jiayang; Chen, Miao; Yan, Bei; Yuan, Qiqiang

    2016-08-01

    Torrefaction of pine wood was performed in a tube furnace at three temperatures (220, 250, and 280°C) for 30min. Then catalytic pyrolysis of raw and torrefied pine wood was performed using HZSM-5 catalyst in a fixed-bed pyrolysis reactor at 550°C for 15min. Torrefaction pretreatment and catalytic pyrolysis have an very important effect on the yield, property, and energy distribution of pyrolysis products. The results showed that the yield of biochar rapidly increased, while that of bio-oil decreased with increasing torrefaction temperature. The oxy-compound content of bio-oil, such as acids and aldehydes, sharply decreased. However, the aromatic hydrocarbon content not only increased but also further promoted by HZSM-5 catalyst. With highest mass yields and energy yields, biochar was also the very important product of pyrolysis. The oxygen content in biomass was mainly removed in the form of CO2 and H2O, leading to increasing CO2 content in non-condensable gas. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Experimental and Numerical Evaluation of the By-Pass Flow in a Catalytic Plate Reactor for Hydrogen Production

    DEFF Research Database (Denmark)

    Sigurdsson, Haftor Örn; Kær, Søren Knudsen

    2011-01-01

    increases. The numerical results are in good agreement with experimental data. The study improves the understanding of the underlying transport phenomena in these reactors and shows that the flow maldistribution in a catalytic plate reactor using a coated wire mesh has to be considered....

  1. Generating hydrogen for mobile devices; Wasserstofferzeugung fuer die mobile Anwendung

    Energy Technology Data Exchange (ETDEWEB)

    Schuetz, W. [Vodafone Pilotentwicklung GmbH, Muenchen (Germany)

    2001-10-01

    In future vehicles, more and more functions will be powered by electricity. These are for example ''steer by wire'', ''break by wire'', air conditioning and infotainment. This growing demand for electricity is a new challenge for the automotive industry. The so called APU (auxilliary power unit) is a convincing solution. This power generating unit based on fuel cell technology will provide electrical power in all operation situations. The article deals with the main focus of P{sup 21}-power for the 21st century, the Mannesmann Fuel Cell Product Center of the Vodafone Pilotentwicklung. (orig.)

  2. Mixing of radiolytic hydrogen generated within a containment compartment following a LOCA

    International Nuclear Information System (INIS)

    Willcutt, G.J.E. Jr.; Gido, R.G.

    1978-07-01

    The objective of this work was to determine hydrogen concentration variations with position and time in a closed containment compartment with radiolytic hydrogen generation in the water on the compartment floor following a Loss-of-Coolant-Accident (LOCA). One application is to determine the potential difference between the compartment maximum hydrogen concentration and a hydrogen detector reading, due to the detector location. Three possible mechanisms for hydrogen transport in the compartment were investigated: (1) molecular diffusion, (2) possible bubble formation and motion, and (3) natural convection flows. A base case cubic compartment with 6.55-m (21.5-ft) height was analyzed. Parameter studies were used to determine the sensitivity of results to compartment size, hydrogen generation rates, diffusion coefficients, and the temperature difference between the floor and the ceiling and walls of the compartment. Diffusion modeling indicates that if no other mixing mechanism is present for the base case, the maximum hydrogen volume percent (vol percent) concentration difference between the compartment floor and ceiling will be 4.8 percent. It will be 24.5 days before the maximum concentration difference is less than 0.5 percent. Bubbles do not appear to be a potential source of hydrogen pocketing in a containment compartment. Compartment natural convection circulation rates for a 2.8 K (5 0 F) temperature difference between the floor and the ceiling and walls are estimated to be at least the equivalent of 1 compartment volume per hour and probably in the range of 4 to 9 compartment volumes per hour. Related natural convection studies indicate there will be turbulent mixing in the compartment for a 2.8 K (5 0 F) temperature difference between the floor and the ceiling and walls

  3. In Situ Catalytic Upgrading of Heavy Crude with CAPRI: Influence of Hydrogen on Catalyst Pore Plugging and Deactivation due to Coke

    Directory of Open Access Journals (Sweden)

    Abarasi Hart

    2018-03-01

    Full Text Available Heavy crude oil is known to have low hydrogen-to-carbon ratios compared to light oil. This is due to the significant content of carbon-rich species such as resins and asphaltenes; hence their upgrading is commonly through carbon-rejection. However, carbon-rejection promotes rapid fouling of catalyst and pore plugging, yielding low upgraded oil and consequently low fuel distillate fractions when distilled. The roles of hydrogen-addition on in situ catalytic upgrading were investigated at pre-established conditions (425 °C, LHSV 11.8 h−1, and 20–40 bars using a simulated fixed-bed reactor that mimics the annular sheath of catalyst (CAPRI surrounding the horizontal producer well of the Toe-to-Heel Air Injection (THAI process. It was found that with H-addition, the upgraded oil American Petroleum Institute (API gravity increased to about 5° compared to 3° obtained with N2 above 13° (THAI feed oil. The fuel distillate fractions increased to 62% (N2, 20 bar, 65% (H2, 20 bar, and 71.8% (H2, 30 bar relative to 40.6% (THAI feed oil; while the coke contents of the catalyst after experiments were 35.3 wt % (N2, and 27.2 wt % (H2. It was also found that catalyst pore plugging and deactivation due to coke was significantly lower under hydrogen than with nitrogen; hence the catalyst is less susceptible to coke fouling when the upgrading reaction is carried out under hydrogen. The coke fouling further decreases with increasing hydrogen pressure while the API gravity of the upgraded oil marginally increases by 0.3° for every 10 bar increase in pressure from 20 to 40 bar.

  4. Catalytic Hydrogenation of Levulinic Acid in Water into g-Valerolactone over Bulk Structure of Inexpensive Intermetallic Ni-Sn Alloy Catalysts

    Directory of Open Access Journals (Sweden)

    Rodiansono Rodiansono

    2015-07-01

    Full Text Available A bulk structure of inexpensive intermetallic nickel-tin (Ni-Sn alloys catalysts demonstrated highly selective in the hydrogenation of levulinic acid in water into g-valerolactone. The intermetallic Ni-Sn catalysts were synthesized via a very simple thermochemical method from non-organometallic precursor at low temperature followed by hydrogen treatment at 673 K for 90 min. The molar ratio of nickel salt and tin salt was varied to obtain the corresponding Ni/Sn ratio of 4.0, 3.0, 2.0, 1.5, and 0.75. The formation of Ni-Sn alloy species was mainly depended on the composition and temperature of H2 treatment. Intermetallics Ni-Sn that contain Ni3Sn, Ni3Sn2, and Ni3Sn4 alloy phases are known to be effective heterogeneous catalysts for levulinic acid hydrogenation giving very excellence g-valerolactone yield of >99% at 433 K, initial H2 pressure of 4.0 MPa within 6 h. The effective hydrogenation was obtained in H2O without the formation of by-product. Intermetallic Ni-Sn(1.5 that contains Ni3Sn2 alloy species demonstrated very stable and reusable catalyst without any significant loss of its selectivity. © 2015 BCREC UNDIP. All rights reserved. Received: 26th February 2015; Revised: 16th April 2015; Accepted: 22nd April 2015  How to Cite: Rodiansono, R., Astuti, M.D., Ghofur, A., Sembiring, K.C. (2015. Catalytic Hydrogenation of Levulinic Acid in Water into g-Valerolactone over Bulk Structure of Inexpensive Intermetallic Ni-Sn Alloy Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 192-200. (doi:10.9767/bcrec.10.2.8284.192-200Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.8284.192-200  

  5. Flow injection determination of hydrogen peroxide using catalytic effect of cobalt(II) ion on a dye formation reaction.

    Science.gov (United States)

    Kurihara, Makoto; Muramatsu, Miyuki; Yamada, Mari; Kitamura, Naoya

    2012-07-15

    A novel flow injection photometric method was developed for the determination of hydrogen peroxide in rainwater. This method is based on a cobalt(II)-catalyzed oxidative coupling of 3-methyl-2-benzothiazolinone hydrazone (MBTH) with N-ethyl-N-(2-hydroxy-3-sulfopropyl)-3,5-dimethoxyaniline (DAOS) as a modified Trinder's reagent to produce intensely colored dye (λ(max)=530nm) in the presence of hydrogen peroxide at pH 8.4. In this method, 1,2-dihydroxy-3,5-benzenedisulfonic acid (Tiron) acted as an activator for the cobalt(II)-catalyzed reaction and effectively increased the peak height for hydrogen peroxide. The linear calibration graphs were obtained in the hydrogen peroxide concentration range 5×10(-8) to 2.2×10(-6)mol dm(-3) at a sampling rate of 20h(-1). The relative standard deviations for ten determinations of 2.2×10(-6) and 2×10(-7)mol dm(-3) hydrogen peroxide were 1.1% and 3.7%, respectively. The proposed method was successfully applied to the determination of hydrogen peroxide in rainwater samples and the analytical results agreed fairly well with the results obtained by different two reference methods; peroxidase method and hydrogen peroxide electrode method. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Hydrogen generation in SRAT with nitric acid and late washing flowsheets

    International Nuclear Information System (INIS)

    Hsu, C.W.

    1992-01-01

    Melter feed preparation processes, incorporating a final wash of the precipitate slurry feed to Defense Waste Processing Facility (DWPF) and a partial substitution of the SRAT formic acid requirement with nitric acid, should not produce peak hydrogen generation rates during Cold Chemical Runs (CCR's) and radioactive operation greater than their current, respective hydrogen design bases of 0.024 lb/hr and 1.5 lb/hr. A single SRAT bench-scale process simulation for CCR-s produced a DWPF equivalent peak hydrogen generation rate of 0.004 lb/hr. During radioactive operation, the peak hydrogen generation rate will be dependent on the extent DWPF deviates from the nominal precipitate hydrolysis and melter feed preparation process operating parameters. Two actual radioactive sludges were treated according to the new flowsheets. The peak hydrogen evolution rates were equivalent to 0.038 and 0.20 lb/hr (DWPF scale) respectively. Compared to the formic acid -- HAN hydrolysis flowsheets, these peak rates were reduced by a factor of 2.5 and 3.4 for Tank 15 and Tank 11 sludges, respectively

  7. WTP Waste Feed Qualification: Hydrogen Generation Rate Measurement Apparatus Testing Report

    Energy Technology Data Exchange (ETDEWEB)

    Stone, M. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Newell, J. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Smith, T. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Pareizs, J. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-06-01

    The generation rate of hydrogen gas in the Hanford tank waste will be measured during the qualification of the staged tank waste for processing in the Hanford Tank Waste Treatment and Immobilization Plant. Based on a review of past practices in measurement of the hydrogen generation, an apparatus to perform this measurement has been designed and tested for use during waste feed qualification. The hydrogen generation rate measurement apparatus (HGRMA) described in this document utilized a 100 milliliter sample in a continuously-purged, continuously-stirred vessel, with measurement of hydrogen concentration in the vent gas. The vessel and lid had a combined 220 milliliters of headspace. The vent gas system included a small condenser to prevent excessive evaporative losses from the sample during the test, as well as a demister and filter to prevent particle migration from the sample to the gas chromatography system. The gas chromatograph was an on line automated instrument with a large-volume sample-injection system to allow measurement of very low hydrogen concentrations. This instrument automatically sampled the vent gas from the hydrogen generation rate measurement apparatus every five minutes and performed data regression in real time. The fabrication of the hydrogen generation rate measurement apparatus was in accordance with twenty three (23) design requirements documented in the conceptual design package, as well as seven (7) required developmental activities documented in the task plan associated with this work scope. The HGRMA was initially tested for proof of concept with physical simulants, and a remote demonstration of the system was performed in the Savannah River National Laboratory Shielded Cells Mockup Facility. Final verification testing was performed using non-radioactive simulants of the Hanford tank waste. Three different simulants were tested to bound the expected rheological properties expected during waste feed qualification testing. These

  8. A third-generation dispersion and third-generation hydrogen bonding corrected PM6 method

    DEFF Research Database (Denmark)

    Kromann, Jimmy Charnley; Christensen, Anders Steen; Svendsen, Casper Steinmann

    2014-01-01

    We present new dispersion and hydrogen bond corrections to the PM6 method, PM6-D3H+, and its implementation in the GAMESS program. The method combines the DFT-D3 dispersion correction by Grimme et al. with a modified version of the H+ hydrogen bond correction by Korth. Overall, the interaction en...... vibrational free energies. While the GAMESS implementation is up to 10 times slower for geometry optimizations of proteins in bulk solvent, compared to MOPAC, it is sufficiently fast to make geometry optimizations of small proteins practically feasible....

  9. Generation of hydrogen rich gas through fluidized bed gasification of biomass.

    Science.gov (United States)

    Karmakar, M K; Datta, A B

    2011-01-01

    The objective of this study was to investigate the process of generating hydrogen rich syngas through thermo chemical fluidized bed gasification of biomass. The experiments were performed in a laboratory scale externally heated biomass gasifier. Rice husk had been taken as a representative biomass and, steam had been used as the fluidizing and gasifying media. A thermodynamic equilibrium model was used to predict the gasification process. The work included the parametric study of process parameters such as reactor temperature and steam biomass ratio which generally influence the percentage of hydrogen content in the product gas. Steam had been used here to generate nitrogen free product gas and also to increase the hydrogen concentration in syngas with a medium range heating value of around 12 MJ/Nm3. Copyright © 2010 Elsevier Ltd. All rights reserved.

  10. Start up system for hydrogen generator used with an internal combustion engine

    Science.gov (United States)

    Houseman, J.; Cerini, D. J. (Inventor)

    1977-01-01

    A hydrogen generator provides hydrogen rich product gases which are mixed with the fuel being supplied to an internal combustion engine for the purpose of enabling a very lean mixture of that fuel to be used, whereby nitrous oxides emitted by the engine are minimized. The hydrogen generator contains a catalyst which must be heated to a pre-determined temperature before it can react properly. To simplify the process of heating up the catalyst at start-up time, either some of the energy produced by the engine such as engine exhaust gas, or electrical energy produced by the engine, or the engine exhaust gas may be used to heat up air which is then used to heat the catalyst.

  11. On the role of metal particle size and surface coverage for photo-catalytic hydrogen production; a case study of the Au/CdS system

    KAUST Repository

    Majeed, I.

    2015-09-25

    Photo-catalytic hydrogen production has been studied on Au supported CdS catalysts under visible light irradiation in order to understand the effect of Au particle size as well as the reaction medium properties. Au nanoparticles of size about 2-5 nm were deposited over hexagonal CdS particles using a new simple method involving reduction of Au3+ ions with iodide ions. Within the investigated range of Au (between 1 and 5 wt. %) fresh particles with mean size of 4 nm and XPS Au4f/Cd3d surface ratio of 0.07 showed the highest performance (ca. 1 molecule of H2 / Auatom s−1) under visible light irradiation (>420 nm and a flux of 35 mW/cm2). The highest hydrogen production rate was obtained from water (92%)-ethanol (8%) in an electrolyte medium (Na2S-Na2SO3). TEM studies of fresh and used catalysts showed that Au particle size increases (almost 5 fold) with increasing photo-irradiation time due to photo-agglomeration effect yet no sign of deactivation was observed. A mechanism for hydrogen production from ethanol-water electrolyte mixture is presented and discussed.

  12. Novel developments in hydrogen storage, hydrogen activation and ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Doroodian, Amir

    2010-12-03

    This dissertation is divided into three chapters. Recently, metal-free hydrogen activation using phosphorous compounds has been reported in science magazine. We have investigated the interaction between hydrogen and phosphorous compounds in presence of strong Lewis acids (chapter one). A new generation of metal-free hydrogen activation, using amines and strong Lewis acids with sterically demanding nature, was already developed in our group. Shortage of high storage capacity using large substitution to improve sterical effect led us to explore the amine borane derivatives, which are explained in chapter two. Due to the high storage capacity of hydrogen in aminoborane derivatives, we have explored these materials to extend hydrogen release. These compounds store hydrogen as proton and hydride on adjacent atoms or ions. These investigations resulted in developing hydrogen storage based on ionic liquids containing methyl guanidinium cation. Then we have continued to develop ionic liquids based on methyl guanidinium cation with different anions, such as tetrafluoro borate (chapter three). We have replaced these anions with transition metal anions to investigate hydrogen bonding and catalytic activity of ionic liquids. This chapter illustrates the world of ionic liquid as a green solvent for organic, inorganic and catalytic reactions and combines the concept of catalysts and solvents based on ionic liquids. The catalytic activity is investigated particularly with respect to the interaction with CO{sub 2}. (orig.)

  13. Sizing Hydrogen Energy Storage in Consideration of Demand Response in Highly Renewable Generation Power Systems

    Directory of Open Access Journals (Sweden)

    Mubbashir Ali

    2018-05-01

    Full Text Available From an environment perspective, the increased penetration of wind and solar generation in power systems is remarkable. However, as the intermittent renewable generation briskly grows, electrical grids are experiencing significant discrepancies between supply and demand as a result of limited system flexibility. This paper investigates the optimal sizing and control of the hydrogen energy storage system for increased utilization of renewable generation. Using a Finnish case study, a mathematical model is presented to investigate the optimal storage capacity in a renewable power system. In addition, the impact of demand response for domestic storage space heating in terms of the optimal sizing of energy storage is discussed. Finally, sensitivity analyses are conducted to observe the impact of a small share of controllable baseload production as well as the oversizing of renewable generation in terms of required hydrogen storage size.

  14. Fuel processor and method for generating hydrogen for fuel cells

    Science.gov (United States)

    Ahmed, Shabbir [Naperville, IL; Lee, Sheldon H. D. [Willowbrook, IL; Carter, John David [Bolingbrook, IL; Krumpelt, Michael [Naperville, IL; Myers, Deborah J [Lisle, IL

    2009-07-21

    A method of producing a H.sub.2 rich gas stream includes supplying an O.sub.2 rich gas, steam, and fuel to an inner reforming zone of a fuel processor that includes a partial oxidation catalyst and a steam reforming catalyst or a combined partial oxidation and stream reforming catalyst. The method also includes contacting the O.sub.2 rich gas, steam, and fuel with the partial oxidation catalyst and the steam reforming catalyst or the combined partial oxidation and stream reforming catalyst in the inner reforming zone to generate a hot reformate stream. The method still further includes cooling the hot reformate stream in a cooling zone to produce a cooled reformate stream. Additionally, the method includes removing sulfur-containing compounds from the cooled reformate stream by contacting the cooled reformate stream with a sulfur removal agent. The method still further includes contacting the cooled reformate stream with a catalyst that converts water and carbon monoxide to carbon dioxide and H.sub.2 in a water-gas-shift zone to produce a final reformate stream in the fuel processor.

  15. Photocatalytic generation of hydrogen under visible light on La2CuO4

    Indian Academy of Sciences (India)

    1043–1048. c Indian Academy of Sciences. Photocatalytic generation of hydrogen under visible light on La2CuO4 .... phase was identified by X-ray diffraction using Cu Kα radi- ation (λ = 0.154178 nm). The diffuse ..... Omeiri S, Allalou N, Rekhila G, Bessekhouad Y and Trari M. 2013 Appl. Nanosci. 1 8. 10. Tiwari S and ...

  16. Low-level hydrogen peroxide generation by unbleached cotton nonwovens: implications for wound healing applications

    Science.gov (United States)

    Greige cotton is an intact plant fiber. The cuticle and primary cell wall near the outer surface of the cotton fiber contains pectin, peroxidases, superoxide dismutase (SOD), and trace metals, which are associated with hydrogen peroxide (H2O2) generation during cotton fiber development. The compon...

  17. Biomass & Natural Gas Based Hydrogen Fuel For Gas Turbine (Power Generation)

    Science.gov (United States)

    Significant progress has been made by major power generation equipment manufacturers in the development of market applications for hydrogen fuel use in gas turbines in recent years. Development of a new application using gas turbines for significant reduction of power plant CO2 e...

  18. Tuning the Surface Composition of Ni/meso-CeO2with Iridium as an Efficient Catalyst for Hydrogen Generation from Hydrous Hydrazine.

    Science.gov (United States)

    Qiu, Yu-Ping; Yin, Hui; Dai, Hao; Gan, Li-Yong; Dai, Hong-Bin; Wang, Ping

    2018-01-24

    Selective decomposition of hydrous hydrazine (N 2 H 4 ⋅H 2 O) over metal catalysts provides a promising means for onboard or portable hydrogen source applications. Studies on N 2 H 4 ⋅H 2 O decomposition catalysts mainly focus on the effects of bulk composition and structure on their performances, instead of the surface-composition-dependent properties. Herein, the synthesis of an Ir-modified Ni/meso-CeO 2 catalyst is reported by using a combination of solution combustion synthesis (SCS) and galvanic replacement methods. A combination of structural characterization, control experiments, and DFT calculations reveals that the Ni-Ir alloy resulting from calcination treatment exerts a profound effect on the catalytic properties. The resulting Ni@Ni-Ir/meso-CeO 2 catalyst shows excellent catalytic performance towards hydrogen generation from N 2 H 4 ⋅H 2 O, which compares favorably with the Ni-Ir bimetallic catalysts reported to date. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Solid-state-reaction synthesis of cotton-like CoB alloy at room temperature as a catalyst for hydrogen generation.

    Science.gov (United States)

    Wang, Xingpu; Liao, Jinyun; Li, Hao; Wang, Hui; Wang, Rongfang

    2016-08-01

    A novel room-temperature solid-state reaction is developed to synthesize cotton-like CoB alloy (CoBSSR) catalysts with a large specific surface area of 222.4m(2)g(-1). In the hydrolysis of ammonia borane catalyzed by the CoBSSR, the rate of hydrogen generation can reach 68.7mLmin(-1) with a turnover frequency (TOF) value of ca. 6.9Lhydrogenmin(-1)gcatalyst(-1) at 25°C. The TOF value is about 2 times as large as that of CoB alloy prepared by a regular solid-state reaction, which is also much higher than those of the CoB catalysts recently reported in the literature. The activation energy of the hydrolysis of ammonia borane catalyzed by the CoBSSR is as low as 22.78kJmol(-1), hinting that the CoBSSR possesses high catalytic activity, which may be attributed to the large specific surface area and the abundant porous structure. The high catalytic performance, good recoverability and low cost of the CoBSSR enable it to be a promissing catalyst condidate in the hydrolysis of ammonia borane for hydrogen production in commercial application. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. EMPIRICAL RATE EQUATION MODEL and RATE CALCULATIONS OF HYDROGEN GENERATION FOR HANFORD TANK WASTE

    International Nuclear Information System (INIS)

    HU, T.A.

    2004-01-01

    Empirical rate equations are derived to estimate hydrogen generation based on chemical reactions, radiolysis of water and organic compounds, and corrosion processes. A comparison of the generation rates observed in the field with the rates calculated for twenty-eight tanks shows agreement within a factor of three. Revision 1 incorporates the available new data to update the equations. It also includes the contribution from total alpha to radiolysis

  1. Iron piano-stool complexes containing NHC ligands outfitted with pendent arms: synthesis, characterization, and screening for catalytic transfer hydrogenation

    Science.gov (United States)

    Parthapratim Das; Thomas Elder; William W. Brennessel; Stephen C. Chmely

    2016-01-01

    Catalysis is a fundamental technology that is widely used in the food, petrochemical, pharmaceutical, and agricultural sectors to produce chemical products on an industrial scale. Well-defined molecular organometallic species are a cornerstone of catalytic methodology, and the activity and selectivity of these complexes can be modulated by judicious choice of metal and...

  2. Kinetics of liquid-phase catalytic heterogeneous protium-tritium isotope exchange with participation of gaseous hydrogen

    International Nuclear Information System (INIS)

    Akulov, G.P.; Snetkova, E.V.; Kayumov, V.G.; Kaminskij, Yu.L.

    1990-01-01

    Reaction rate constants of catalytic (PdO/BaSO 4 (Al 2 O 3 ) catalyst) heterogeneous protium - tritium isotopic exchange D - [1- 3 H] of carbohydrates and gaseous oxygen have been measured. It is ascertained that the rate of isotopic exchange depends on the nature of carbohydrate, catalyst, buffer and medium acidity. The value of concentration of carbohydrate acyclic forms plays the determining role in the process

  3. Fabrication of efficient TiO2-RGO heterojunction composites for hydrogen generation via water-splitting: Comparison between RGO, Au and Pt reduction sites

    Science.gov (United States)

    El-Bery, Haitham M.; Matsushita, Yoshihisa; Abdel-moneim, Ahmed

    2017-11-01

    A facile one-step synthesis approach of M/TiO2/RGO (M = Au or Pt) ternary composite by hydrothermal treatment for hydrogen generation via water-splitting was investigated. Photocurrent response measurements revealed that TiO2 (P25) nanoparticles anchored on the reduced graphene oxide (RGO) surface exhibited a p-n heterojunction interface by changing the photocurrent direction with the applied bias from reverse to forward potential. H2 evolution rate of TiO2/RGO (5 wt.%) composite was substantially enhanced by 12-fold in comparison to bare TiO2 under simulated solar light irradiation. Cyclic volatmmetry measurements manifested, that the optimized 0.3 wt.% of platinum metal loaded on TiO2/RGO composite was the most active catalytic reduction sites for hydrogen generation reaction with an initial hydrogen rate of 670 μmol h-1. This study sheds the light on the tunable semiconductor type of TiO2/RGO composite fabricated by solution mixing pathway and its merits to improve the photocatalytic activity.

  4. A polymer electrolyte fuel cell stack for stationary power generation from hydrogen fuel

    Energy Technology Data Exchange (ETDEWEB)

    Gottesfeld, S. [Los Alamos National Lab., NM (United States)

    1995-09-01

    The fuel cell is the most efficient device for the conversion of hydrogen fuel to electric power. As such, the fuel cell represents a key element in efforts to demonstrate and implement hydrogen fuel utilization for electric power generation. The low temperature, polymer electrolyte membrane fuel cell (PEMFC) has recently been identified as an attractive option for stationary power generation, based on the relatively simple and benign materials employed, the zero-emission character of the device, and the expected high power density, high reliability and low cost. However, a PEMFC stack fueled by hydrogen with the combined properties of low cost, high performance and high reliability has not yet been demonstrated. Demonstration of such a stack will remove a significant barrier to implementation of this advanced technology for electric power generation from hydrogen. Work done in the past at LANL on the development of components and materials, particularly on advanced membrane/electrode assemblies (MEAs), has contributed significantly to the capability to demonstrate in the foreseeable future a PEMFC stack with the combined characteristics described above. A joint effort between LANL and an industrial stack manufacturer will result in the demonstration of such a fuel cell stack for stationary power generation. The stack could operate on hydrogen fuel derived from either natural gas or from renewable sources. The technical plan includes collaboration with a stack manufacturer (CRADA). It stresses the special requirements from a PEMFC in stationary power generation, particularly maximization of the energy conversion efficiency, extension of useful life to the 10 hours time scale and tolerance to impurities from the reforming of natural gas.

  5. Insight into the mechanism revealing the peroxidase mimetic catalytic activity of quaternary CuZnFeS nanocrystals: colorimetric biosensing of hydrogen peroxide and glucose

    Science.gov (United States)

    Dalui, Amit; Pradhan, Bapi; Thupakula, Umamahesh; Khan, Ali Hossain; Kumar, Gundam Sandeep; Ghosh, Tanmay; Satpati, Biswarup; Acharya, Somobrata

    2015-05-01

    Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been evaluated by catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). CZIS NCs demonstrate the synergistic effect of elemental composition and photoactivity towards peroxidase-like activity. The quaternary CZIS NCs show enhanced intrinsic peroxidase-like activity compared to the binary NCs with the same constituent elements. Intrinsic peroxidase-like activity has been correlated with the energy band position of CZIS NCs extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. Kinetic analyses indicate Michaelis-Menten enzyme kinetic model catalytic behavior describing the rate of the enzymatic reaction by correlating the reaction rate with substrate concentration. Typical color reactions arising from the catalytic oxidation of TMB over CZIS NCs with H2O2 have been utilized to establish a simple and sensitive colorimetric assay for detection of H2O2 and glucose. CZIS NCs are recyclable catalysts showing high efficiency in multiple uses. Our study may open up the possibility of designing new photoactive multi-component alloyed NCs as enzyme mimetics in biotechnology applications.Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been

  6. NOBLE METAL CHEMISTRY AND HYDROGEN GENERATION DURING SIMULATED DWPF MELTER FEED PREPARATION

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-06-25

    Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell vessels were performed with the primary purpose of producing melter feeds for the beaded frit program plus obtaining samples of simulated slurries containing high concentrations of noble metals for off-site analytical studies for the hydrogen program. Eight pairs of 22-L simulations were performed of the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles. These sixteen simulations did not contain mercury. Six pairs were trimmed with a single noble metal (Ag, Pd, Rh, or Ru). One pair had all four noble metals, and one pair had no noble metals. One supporting 4-L simulation was completed with Ru and Hg. Several other 4-L supporting tests with mercury have not yet been performed. This report covers the calculations performed on SRNL analytical and process data related to the noble metals and hydrogen generation. It was originally envisioned as a supporting document for the off-site analytical studies. Significant new findings were made, and many previous hypotheses and findings were given additional support as summarized below. The timing of hydrogen generation events was reproduced very well within each of the eight pairs of runs, e.g. the onset of hydrogen, peak in hydrogen, etc. occurred at nearly identical times. Peak generation rates and total SRAT masses of CO{sub 2} and oxides of nitrogen were reproduced well. Comparable measures for hydrogen were reproduced with more variability, but still reasonably well. The extent of the reproducibility of the results validates the conclusions that were drawn from the data.

  7. Effect of Copper Nanoparticles Dispersion on Catalytic Performance of Cu/SiO2 Catalyst for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol

    Directory of Open Access Journals (Sweden)

    Yajing Zhang

    2013-01-01

    Full Text Available Cu/SiO2 catalysts, for the synthesis of ethylene glycol (EG from hydrogenation of dimethyl oxalate (DMO, were prepared by ammonia-evaporation and sol-gel methods, respectively. The structure, size of copper nanoparticles, copper dispersion, and the surface chemical states were investigated by X-ray diffraction (XRD, transmission electron microscopy (TEM, temperature-programmed reduction (TPR, and X-ray photoelectron spectroscopy (XPS and N2 adsorption. It is found the structures and catalytic performances of the catalysts were highly affected by the preparation method. The catalyst prepared by sol-gel method had smaller average size of copper nanoparticles (about 3-4 nm, better copper dispersion, higher Cu+/C0 ratio and larger BET surface area, and higher DMO conversion and EG selectivity under the optimized reaction conditions.

  8. Anaerobic digestion for methane generation and ammonia reforming for hydrogen production: A thermodynamic energy balance of a model system to demonstrate net energy feasibility

    International Nuclear Information System (INIS)

    Babson, David M.; Bellman, Karen; Prakash, Shaurya; Fennell, Donna E.

    2013-01-01

    During anaerobic digestion, organic matter is converted to carbon dioxide and methane, and organic nitrogen is converted to ammonia. Generally, ammonia is recycled as a fertilizer or removed via nitrification–denitrification in treatment systems; alternatively it could be recovered and catalytically converted to hydrogen, thus supplying additional fuel. To provide a basis for further investigation, a theoretical energy balance for a model system that incorporates anaerobic digestion, ammonia separation and recovery, and conversion of the ammonia to hydrogen is reported. The model Anaerobic Digestion-Bioammonia to Hydrogen (ADBH) system energy demands including heating, pumping, mixing, and ammonia reforming were subtracted from the total energy output from methane and hydrogen to create an overall energy balance. The energy balance was examined for the ADBH system operating with a fixed feedstock loading rate with C:N ratios (gC/gN) ranging from 136 to 3 which imposed corresponding total ammonia nitrogen (TAN) concentrations of 20–10,000 mg/L. Normalizing total energy potential to the methane potential alone indicated that at a C:N ratio of 17, the energy output was greater for the ADBH system than from anaerobic digestion generating only methane. Decreasing the C:N ratio increased the methane content of the biogas comprising primarily methane to >80% and increased the ammonia stripping energy demand. The system required 23–34% of the total energy generated as parasitic losses with no energy integration, but when internally produced heat and pressure differentials were recovered, parasitic losses were reduced to between 8 and 17%. -- Highlights: •Modeled an integrated Anaerobic Digestion-Bioammonia to Hydrogen (ADBH) system. •Demonstrated positive net energy produced over a range of conditions by ADBH. •Demonstrated significant advantages of dual fuel recovery for energy gain by >20%. •Suggested system design considerations for energy recovery with

  9. High Efficiency Generation of Hydrogen Fuels Using Solar Thermochemical Splitting of Water

    Energy Technology Data Exchange (ETDEWEB)

    Heske, Clemens; Moujaes, Samir; Weimer, Alan; Wong, Bunsen; Siegal, Nathan; McFarland, Eric; Miller, Eric; Lewis, Michele; Bingham, Carl; Roth, Kurth; Sabacky, Bruce; Steinfeld, Aldo

    2011-09-29

    The objective of this work is to identify economically feasible concepts for the production of hydrogen from water using solar energy. The ultimate project objective was to select one or more competitive concepts for pilot-scale demonstration using concentrated solar energy. Results of pilot scale plant performance would be used as foundation for seeking public and private resources for full-scale plant development and testing. Economical success in this venture would afford the public with a renewable and limitless source of energy carrier for use in electric power load-leveling and as a carbon-free transportation fuel. The Solar Hydrogen Generation Research (SHGR) project embraces technologies relevant to hydrogen research under the Office of Hydrogen Fuel Cells and Infrastructure Technology (HFCIT) as well as concentrated solar power under the Office of Solar Energy Technologies (SET). Although the photoelectrochemical work is aligned with HFCIT, some of the technologies in this effort are also consistent with the skills and technologies found in concentrated solar power and photovoltaic technology under the Office of Solar Energy Technologies (SET). Hydrogen production by thermo-chemical water-splitting is a chemical process that accomplishes the decomposition of water into hydrogen and oxygen using only heat or a combination of heat and electrolysis instead of pure electrolysis and meets the goals for hydrogen production using only water and renewable solar energy as feed-stocks. Photoelectrochemical hydrogen production also meets these goals by implementing photo-electrolysis at the surface of a semiconductor in contact with an electrolyte with bias provided by a photovoltaic source. Here, water splitting is a photo-electrolytic process in which hydrogen is produced using only solar photons and water as feed-stocks. The thermochemical hydrogen task engendered formal collaborations among two universities, three national laboratories and two private sector

  10. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion

    OpenAIRE

    Tanabe, Katsuaki

    2016-01-01

    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any com...

  11. Comparative study of the hydrogen generation during short term station blackout (STSBO) in a BWR

    International Nuclear Information System (INIS)

    Polo-Labarrios, M.A.; Espinosa-Paredes, G.

    2015-01-01

    Highlights: • Comparative study of generation in a simulated STSBO severe accident. • MELCOR and SCDAP/RELAP5 codes were used to understanding the main phenomena. • Both codes present similar thermal-hydraulic behavior for pressure and boil off. • SCDAP/RELAP5 predicts 15.8% lower hydrogen production than MELCOR. - Abstract: The aim of this work is the comparative study of hydrogen generation and the associated parameters in a simulated severe accident of a short-term station blackout (STSBO) in a typical BWR-5 with Mark-II containment. MELCOR (v.1.8.6) and SCDAP/RELAP5 (Mod.3.4) codes were used to understand the main phenomena in the STSBO event through the results comparison obtained from simulations with these codes. Due that the simulation scope of SCDAP/RELAP5 is limited to failure of the vessel pressure boundary, the comparison was focused on in-vessel severe accident phenomena; with a special interest in the vessel pressure, boil of cooling, core temperature, and hydrogen generation. The results show that at the beginning of the scenario, both codes present similar thermal-hydraulic behavior for pressure and boil off of cooling, but during the relocation, the pressure and boil off, present differences in timing and order of magnitude. Both codes predict in similar time the beginning of melting material drop to the lower head. As far as the hydrogen production rate, SCDAP/RELAP5 predicts 15.8% lower production than MELCOR

  12. Large area imaging of hydrogenous materials using fast neutrons from a DD fusion generator

    Science.gov (United States)

    Cremer, J. T.; Williams, D. L.; Gary, C. K.; Piestrup, M. A.; Faber, D. R.; Fuller, M. J.; Vainionpaa, J. H.; Apodaca, M.; Pantell, R. H.; Feinstein, J.

    2012-05-01

    A small-laboratory fast-neutron generator and a large area detector were used to image hydrogen-bearing materials. The overall image resolution of 2.5 mm was determined by a knife-edge measurement. Contact images of objects were obtained in 5-50 min exposures by placing them close to a plastic scintillator at distances of 1.5 to 3.2 m from the neutron source. The generator produces 109 n/s from the DD fusion reaction at a small target. The combination of the DD-fusion generator and electronic camera permits both small laboratory and field-portable imaging of hydrogen-rich materials embedded in high density materials.

  13. Large area imaging of hydrogenous materials using fast neutrons from a DD fusion generator

    International Nuclear Information System (INIS)

    Cremer, J.T.; Williams, D.L.; Gary, C.K.; Piestrup, M.A.; Faber, D.R.; Fuller, M.J.; Vainionpaa, J.H.; Apodaca, M.; Pantell, R.H.; Feinstein, J.

    2012-01-01

    A small-laboratory fast-neutron generator and a large area detector were used to image hydrogen-bearing materials. The overall image resolution of 2.5 mm was determined by a knife-edge measurement. Contact images of objects were obtained in 5–50 min exposures by placing them close to a plastic scintillator at distances of 1.5 to 3.2 m from the neutron source. The generator produces 10 9 n/s from the DD fusion reaction at a small target. The combination of the DD-fusion generator and electronic camera permits both small laboratory and field-portable imaging of hydrogen-rich materials embedded in high density materials.

  14. Thermodynamic analysis of a solar-based multi-generation system with hydrogen production

    International Nuclear Information System (INIS)

    Ozturk, Murat; Dincer, Ibrahim

    2013-01-01

    Thermodynamic analysis of a renewable-based multi-generation energy production system which produces a number of outputs, such as power, heating, cooling, hot water, hydrogen and oxygen is conducted. This solar-based multi-generation system consists of four main sub-systems: Rankine cycle, organic Rankine cycle, absorption cooling and heating, and hydrogen production and utilization. Exergy destruction ratios and rates, power or heat transfer rates, energy and exergy efficiencies of the system components are carried out. Some parametric studies are performed in order to examine the effects of varying operating conditions (e.g., reference temperature, direct solar radiation and receiver temperature) on the exergy efficiencies of the sub-systems as well as the whole system. The solar-based multi-generation system which has an exergy efficiency of 57.35%, is obtained to be higher than using these sub-systems separately. The evaluation of the exergy efficiency and exergy destruction for the sub-systems and the overall system show that the parabolic dish collectors have the highest exergy destruction rate among constituent parts of the solar-based multi-generation system, due to high temperature difference between the working fluid and collector receivers. -- Highlights: ► Development of a new multi-generation system for solar-based hydrogen production. ► Investigation of exergy efficiencies and destructions in each process of the system. ► Evaluation of varying operating conditions on the exergy destruction and efficiency

  15. Alkali free hydrolysis of sodium borohydride for hydrogen generation under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, M.J.F.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto (Portugal); Gales, L. [Instituto de Biologia Molecular e Celular, Universidade do Porto, Rua do Campo Alegre 823, 4150-180 Porto and Instituto de Ciencias Biomedicas Abel Salazar, Largo Prof. Abel Salazar 2, 4099-003 Porto (Portugal); Fernandes, V.R.; Rangel, C.M. [Laboratorio Nacional de Energia e Geologia - LNEG, Fuel Cells and Hydrogen Unit Estrada do Paco do Lumiar 22, 1649-038 Lisboa (Portugal)

    2010-09-15

    The present study is related with the production of hydrogen gas (H{sub 2}), at elevated pressures and with high gravimetric storage density, to supply a PEM fuel cell on-demand. To achieve this goal, solid sodium borohydride (NaBH{sub 4}) was mixed with a proper amount of a powder reused nickel-ruthenium based catalyst (Ni-Ru based/NaBH{sub 4}: 0.2 and 0.4 g/g; {approx}150 times reused) inside the bottom of a batch reactor. Then, a stoichiometric amount of pure liquid water (H{sub 2}O/NaBH{sub 4}: 2-8 mol/mol) was added and the catalyzed NaBH{sub 4} hydrolysis evolved, in the absence of an alkali inhibitor. In this way, this research work is designated alkali free hydrolysis of NaBH{sub 4} for H{sub 2} generation. This type of hydrolysis is excellent from an environmental point of view because it does not involve strongly caustic solutions. Experiments were performed in three batch reactors with internal volumes 646, 369 and 229 cm{sup 3}, and having different bottom geometries (flat and conical shapes). The H{sub 2} generated was a function of the added water and completion was achieved with H{sub 2}O/NaBH{sub 4} = 8 mol/mol. The results show that hydrogen yields and rates increase remarkably increasing both system temperature and pressure. Reactor bottom shape influences deeply H{sub 2} generation: the conical bottom shape greatly enhances the rate and practically eliminates the reaction induction time. Our system of compressed hydrogen generation up to 1.26 MPa shows 6.3 wt% and 70 kg m{sup -3}, respectively, for gravimetric and volumetric hydrogen storage capacities (materials-only basis) and therefore is a viable hydrogen storage candidate for portable applications. (author)

  16. Plasma-assisted catalytic ionization using porous nickel plate

    International Nuclear Information System (INIS)

    Oohara, W.; Maeda, T.; Higuchi, T.

    2011-01-01

    Hydrogen atomic pair ions, i.e., H + and H - ions, are produced by plasma-assisted catalytic ionization using a porous nickel plate. Positive ions in a hydrogen plasma generated by dc arc discharge are irradiated to the porous plate, and pair ions are produced from the back of the irradiation plane. It becomes clear that the production quantity of pair ions mainly depends on the irradiation current of positive ions and the irradiation energy affects the production efficiency of H - ions.

  17. Hydrogen Generation by Koh-Ethanol Plasma Electrolysis Using Double Compartement Reactor

    Science.gov (United States)

    Saksono, Nelson; Sasiang, Johannes; Dewi Rosalina, Chandra; Budikania, Trisutanti

    2018-03-01

    This study has successfully investigated the generation of hydrogen using double compartment reactor with plasma electrolysis process. Double compartment reactor is designed to achieve high discharged voltage, high concentration, and also reduce the energy consumption. The experimental results showed the use of double compartment reactor increased the productivity ratio 90 times higher compared to Faraday electrolysis process. The highest hydrogen production obtained is 26.50 mmol/min while the energy consumption can reach up 1.71 kJ/mmol H2 at 0.01 M KOH solution. It was shown that KOH concentration, addition of ethanol, cathode depth, and temperature have important effects on hydrogen production, energy consumption, and process efficiency.

  18. Ferrous ion as a reducing agent in the generation of antibiofilm nitric oxide from a copper-based catalytic system.

    Science.gov (United States)

    Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

    2018-01-31

    The work found that the electron-donating properties of ferrous ions (Fe 2+ ) can be used for the conversion of nitrite (NO 2 - ) into the biofilm-dispersing signal nitric oxide (NO) by a copper(II) complex (CuDTTCT) catalyst, a potentially applicable biofilm control technology for the water industries. The availability of Fe 2+ varied depending on the characteristics of the aqueous systems (phosphate- and carbonate-containing nitrifying bacteria growth medium, NBGM and phosphate buffered saline, PBS at pH 6 to 8, to simulate conditions typically present in the water industries) and was found to affect the production of NO from nitrite by CuDTTCT (casted into PVC). Greater amounts of NO were generated from the CuDTTCT-nitrite-Fe 2+ systems in PBS compared to those in NBGM, which was associated with the reduced extent of Fe 2+ -to-Fe 3+ autoxidation by the iron-precipitating moieties phosphates and carbonate in the former system. Further, acidic conditions at pH 6.0 were found to favor NO production from the catalytic system in both PBS and NBGM compared to neutral or basic pH (pH 7.0 or 8.0). Lower pH was shown to stabilize Fe 2+ and reduce its autoxidation to Fe 3+ . These findings will be beneficial for the potential implementation of the NO-generating catalytic technology and indeed, a 'non-killing' biofilm dispersal activity of CuDTTCT-nitrite-Fe 2+ was observed on nitrifying bacteria biofilms in PBS at pH 6. Copyright © 2018 Elsevier Inc. All rights reserved.

  19. Production of Hydrogen from Bio-ethanol

    International Nuclear Information System (INIS)

    Fabrice Giroudiere; Christophe Boyer; Stephane His; Robert Sanger; Kishore Doshi; Jijun Xu

    2006-01-01

    IFP and HyRadix are collaborating in the development of a new hydrogen production system from liquid feedstock such as bio-ethanol. Reducing greenhouse gas (GHG) emissions along with high hydrogen yield are the key objectives. Market application of the system will be hydrogen refueling stations as well as medium scale hydrogen consumers including the electronics, metals processing, and oils hydrogenation industries. The conversion of bio-ethanol to hydrogen will be performed within a co-developed process including an auto-thermal reformer working under pressure. The technology will produce high-purity hydrogen with ultralow CO content. The catalytic auto-thermal reforming technology combines the exothermic and endothermic reaction and leads to a highly efficient heat integration. The development strategy to reach a high hydrogen yield target with the bio-ethanol hydrogen generator is presented. (authors)

  20. Ni(0-CMC-Na Nickel Colloids in Sodium Carboxymethyl-Cellulose: Catalytic Evaluation in Hydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Abdallah Karim

    2011-01-01

    Full Text Available A recyclable catalyst, Ni(0-CMC-Na, composed of nickel colloids dispersed in a water soluble bioorganic polymer, sodium carboxymethylcellulose (CMC-Na, was synthesized by a simple procedure from readily available reagents. The catalyst thus obtained is stable and highly active in alkene hydrogenations.

  1. Synthesis of (R)-BINOL-Derived (Cyclopentadienone)iron Complexes and Their Application in the Catalytic Asymmetric Hydrogenation of Ketones

    NARCIS (Netherlands)

    Gajewski, Piotr; Renom-Carrasco, Marc; Facchini, Sofia Vailati; Pignataro, Luca; Lefort, Laurent; de Vries, Johannes G.; Ferraccioli, Raffaella; Piarulli, Umberto; Gennari, Cesare

    A family of chiral (cyclopentadienone)iron complexes, featuring an (R)-BINOL-derived backbone, and their application in the asymmetric hydrogenation of ketones are described. The complexes differ from each other in the substituents at the 3,3-positions of the binaphthyl residue (H, OH, OR, OCOR,

  2. The Pt-enriched PtNi alloy surface and its excellent catalytic performance in hydrolytic hydrogenation of cellulose.

    Science.gov (United States)

    Liang, Guanfeng; He, Limin; Arai, Masahiko; Zhao, Fengyu

    2014-05-01

    Ni-based catalysts are currently a subject of intense research in the hydrolytic hydrogenation of cellulose. We previously reported that Ni/ZSM-5 catalyst gave high yield of hexitols. However, Ni-based catalysts suffered fast deactivation in hot-compressed water. In this follow-up study we designed highly active Ni-based bimetallic catalysts with excellent hydrothermal stability for the hydrolytic hydrogenation of microcrystalline cellulose. PtNi/ZSM-5 shows a 76.9 % yield of hexitols, which is the best obtained so far in the hydrolytic hydrogenation of microcrystalline cellulose over Ni-based catalysts. Furthermore, the yield of hexitols remained greater than 55 % after the catalyst was reused for 4 times. The results showed that PtNi nanoparticles were formed with a Pt-enriched alloy surface as confirmed by XRD, H2-TPR (temperature-programmed H2 reduction), XPS (X-ray photoelectron spectroscopy), and H2-TPD (temperature-programmed H2 desorption). The surface features of these nano-particles were characterized by CO-TPD (temperature-programmed CO desorption), CO-FTIR (CO adsorption FTIR spectroscopy), HRTEM (high resolution TEM), and O2-TPO (temperature programmed oxidation) and this special surface structure may be responsible for the high activity, selectivity, and stability in the hydrolytic hydrogenation of cellulose in hot-compressed water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Hydrogen Assisted Cracking in Pearlitic Steel Rods: The Role of Residual Stresses Generated by Fatigue Precracking.

    Science.gov (United States)

    Toribio, Jesús; Aguado, Leticia; Lorenzo, Miguel; Kharin, Viktor

    2017-05-02

    Stress corrosion cracking (SCC) of metals is an issue of major concern in engineering since this phenomenon causes many catastrophic failures of structural components in aggressive environments. SCC is even more harmful under cathodic conditions promoting the phenomenon known as hydrogen assisted cracking (HAC), hydrogen assisted fracture (HAF) or hydrogen embrittlement (HE). A common way to assess the susceptibility of a given material to HAC, HAF or HE is to subject a cracked rod to a constant extension rate tension (CERT) test until it fractures in this harsh environment. This paper analyzes the influence of a residual stress field generated by fatigue precracking on the sample's posterior susceptibility to HAC. To achieve this goal, numerical simulations were carried out of hydrogen diffusion assisted by the stress field. Firstly, a mechanical simulation of the fatigue precracking was developed for revealing the residual stress field after diverse cyclic loading scenarios and posterior stress field evolution during CERT loading. Afterwards, a simulation of hydrogen diffusion assisted by stress was carried out considering the residual stresses after fatigue and the superposed rising stresses caused by CERT loading. Results reveal the key role of the residual stress field after fatigue precracking in the HAC phenomena in cracked steel rods as well as the beneficial effect of compressive residual stress.

  4. On-board hydrogen generation for transport applications: the HotSpot™ methanol processor

    Science.gov (United States)

    Edwards, Neil; Ellis, Suzanne R.; Frost, Jonathan C.; Golunski, Stanislaw E.; van Keulen, Arjan N. J.; Lindewald, Nicklas G.; Reinkingh, Jessica G.

    In the absence of a hydrogen infrastructure, development of effective on-board fuel processors is likely to be critical to the commercialisation of fuel-cell cars. The HotSpot™ reactor converts methanol, water and air in a single compact catalyst bed into a reformate containing mainly CO2 and hydrogen (and unreacted nitrogen). The process occurs by a combination of exothermic partial oxidation and endothermic steam reforming of methanol, to produce 750 l of hydrogen per hour from a 245-cm3 reactor. The relative contribution of each reaction can be tuned to match the system requirements at a given time. Scale-up is achieved by the parallel combination of the required number of individual HotSpot reactors, which are fed from a central manifold. Using this modular design, the start-up and transient characteristics of a large fuel-processor are identical to that of a single reactor. When vaporised liquid feed and air are introduced into cold reactors, 100% output is achieved in 50 s; subsequent changes in throughput result in instantaneous changes in output. Surplus energy within the fuel-cell powertrain can be directed to the manifold, where it can be used to vaporise the liquid feeds and so promote steam reforming, resulting in high system efficiency. The small amount of CO that is produced by the HotSpot reactions is attenuated to <10 ppm by a catalytic clean-up unit. The HotSpot concept and CO clean-up strategy are not limited to the processing of methanol, but are being applied to other organic fuels.

  5. Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

    Science.gov (United States)

    Sun, Tonghua; Shen, Yafei; Jia, Jinping

    2014-02-18

    This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

  6. Catalytic activity of hydrophobic Pt/C/PTFE catalysts of different PTFE content for hydrogen-water liquid exchange reaction

    International Nuclear Information System (INIS)

    Hu Sheng; Xiao Chengjian; Zhu Zuliang; Luo Shunzhong; Wang Heyi; Luo Yangming; Wang Changbin

    2007-01-01

    10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of Pt/C/PTFE catalysts decreases when the mass ratio of PTFE and Pt/C is 0.5:1, and their activity decreases when the mass ratio is 1:1. (authors)

  7. Hydrogen generation from water using Mg nanopowder produced by arc plasma method

    Directory of Open Access Journals (Sweden)

    Masahiro Uda, Hideo Okuyama, Tohru S Suzuki and Yoshio Sakka

    2012-01-01

    Full Text Available We report that hydrogen gas can be easily produced from water at room temperature using a Mg nanopowder (30–1000 nm particles, average diameter 265 nm. The Mg nanopowder was produced by dc arc melting of a Mg ingot in a chamber with mixed-gas atmosphere (20% N2–80% Ar at 0.1 MPa using custom-built nanopowder production equipment. The Mg nanopowder was passivated with a gas mixture of 1% O2 in Ar for 12 h in the final step of the synthesis, after which the nanopowder could be safely handled in ambient air. The nanopowder vigorously reacted with water at room temperature, producing 110 ml of hydrogen gas per 1 g of powder in 600 s. This amount corresponds to 11% of the hydrogen that could be generated by the stoichiometric reaction between Mg and water. Mg(OH2 flakes formed on the surface of the Mg particles as a result of this reaction. They easily peeled off, and the generation of hydrogen continued until all the Mg was consumed.

  8. Hydrogen generation from deliquescence of ammonia borane using Ni-Co/r-GO catalyst

    Science.gov (United States)

    Chou, Chang-Chen; Chen, Bing-Hung

    2015-10-01

    Hydrogen generation from the catalyzed deliquescence/hydrolysis of ammonia borane (AB) using the Ni-Co catalyst supported on the graphene oxide (Ni-Co/r-GO catalyst) under the conditions of limited water supply was studied with the molar feed ratio of water to ammonia borane (denoted as H2O/AB) at 2.02, 3.97 and 5.93, respectively. The conversion efficiency of ammonia borane to hydrogen was estimated both from the cumulative volume of the hydrogen gas generated and the conversion of boron chemistry in the hydrolysates analyzed by the solid-state 11B NMR. The conversion efficiency of ammonia borane could reach nearly 100% under excess water dosage, that is, H2O/AB = 3.97 and 5.93. Notably, the hydrogen storage capacity could reach as high as 6.5 wt.% in the case with H2O/AB = 2.02. The hydrolysates of ammonia borane in the presence of Ni-Co/r-GO catalyst were mainly the mixture of boric acid and metaborate according to XRD, FT-IR and solid-state 11B NMR analyses.

  9. Oxygen dependency of one-electron reactions generating ascorbate radicals and hydrogen peroxide from ascorbic acid.

    Science.gov (United States)

    Boatright, William L

    2016-04-01

    The effect of oxygen on the two separate one-electron reactions involved in the oxidation of ascorbic acid was investigated. The rate of ascorbate radical (Asc(-)) formation (and stability) was strongly dependent on the presence of oxygen. A product of ascorbic acid oxidation was measurable levels of hydrogen peroxide, as high as 32.5 μM from 100 μM ascorbic acid. Evidence for a feedback mechanism where hydrogen peroxide generated during the oxidation of ascorbic acid accelerates further oxidation of ascorbic acid is also presented. The second one-electron oxidation reaction of ascorbic acid leading to the disappearance of Asc(-) was also strongly inhibited in samples flushed with argon. In the range of 0.05-1.2 mM ascorbic acid, maximum levels of measurable hydrogen peroxide were achieved with an initial concentration of 0.2 mM ascorbic acid. Hydrogen peroxide generation was greatly diminished at ascorbic acid levels of 0.8 mM or above. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Rapid hydrogen gas generation using reactive thermal decomposition of uranium hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Kanouff, Michael P.; Van Blarigan, Peter; Robinson, David B.; Shugard, Andrew D.; Gharagozloo, Patricia E.; Buffleben, George M.; James, Scott Carlton; Mills, Bernice E.

    2011-09-01

    Oxygen gas injection has been studied as one method for rapidly generating hydrogen gas from a uranium hydride storage system. Small scale reactors, 2.9 g UH{sub 3}, were used to study the process experimentally. Complimentary numerical simulations were used to better characterize and understand the strongly coupled chemical and thermal transport processes controlling hydrogen gas liberation. The results indicate that UH{sub 3} and O{sub 2} are sufficiently reactive to enable a well designed system to release gram quantities of hydrogen in {approx} 2 seconds over a broad temperature range. The major system-design challenge appears to be heat management. In addition to the oxidation tests, H/D isotope exchange experiments were performed. The rate limiting step in the overall gas-to-particle exchange process was found to be hydrogen diffusion in the {approx}0.5 {mu}m hydride particles. The experiments generated a set of high quality experimental data; from which effective intra-particle diffusion coefficients can be inferred.

  11. Self-Sustained Flameless Heat Generator Based on Catalytic Oxidation of Methane or Propane-Butane Mixture for Various Object Heating Including Field Heating

    Directory of Open Access Journals (Sweden)

    Strizhak, P.Ye.

    2016-09-01

    Full Text Available An effective catalyst based on ceramic block support with honeycomb structure made of synthetic cordierite with low coefficient of temperature linear expansion has been developed. Flameless heat generator based on oxidation of methane or propane-butane mixture has been designed. Laboratory and bench testing revealed that the effectiveness of the generators is identical to foreign analogues. The production of self-sustained flameless heat catalytic generators and the catalysts have been adjusted.

  12. Final Technical Report "Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation" Grant number : DE-FG02-86ER13615

    Energy Technology Data Exchange (ETDEWEB)

    Wayland, B.B.

    2009-08-31

    Title: Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. (wayland@sas.upenn.edu) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbon monoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a central goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory

  13. Experimental, kinetic and numerical modeling of hydrogen production by catalytic reforming of crude ethanol over a commercial catalyst in packed bed tubular reactor and packed bed membrane reactor

    International Nuclear Information System (INIS)

    Aboudheir, Ahmed; Akande, Abayomi; Idem, Raphael

    2006-01-01

    The demand for hydrogen energy has increased tremendously in recent years essentially because of the increase in the word energy consumption as well as recent developments in fuel cell technologies. The energy information administration has projected that world energy consumption will increase by 59% over the next two decades, from 1999 to 2020, in which the largest share is still dominated by fossil fuels (oil, natural gas and coal). Carbon dioxide (CO 2 ) emissions resulting from the combustion of these fossil fuels currently are estimated to account for three-fourth of human-caused CO 2 emissions worldwide. Greenhouse gas emission, including CO 2 , should be limited, as recommended at the Kyoto Conference, Japan, in December 1997. In this regard, hydrogen (H 2 ) has a significant future potential as an alternative fuel that can solve the problems of CO 2 emissions as well as the emissions of other air contaminants. One of the techniques to produce hydrogen is by reforming of hydrocarbons or biomass. Crude ethanol (a form of biomass, which essentially is fermentation broth) is easy to produce, is free of sulphur, has low toxicity, and is also safe to handle, transport and store. In addition, crude ethanol consists of oxygenated hydrocarbons, such as ethanol, lactic acid, glycerol, and maltose. These oxygenated hydrocarbons can be reformed completely to H 2 and CO 2 , the latter of which could be separated from H 2 by membrane technology. This provides for CO 2 capture for eventual storage or destruction. In the case of using crude ethanol, this will result in negative CO 2 , emissions. In this paper, we conducted experimental work on production of hydrogen by the catalytic reforming of crude ethanol over a commercial promoted Ni-based catalyst in a packed bed tubular reactor as well as a packed bed membrane reactor. As well, a rigorous numerical model was developed to simulate this process in both the catalytic packed bed tubular reactor and packed bed membrane

  14. New Ru(II)N'NN'-type pincer complexes: synthesis, characterization and the catalytic hydrogenation of CO2 or bicarbonates to formate salts

    International Nuclear Information System (INIS)

    Zengjin Dai; Qi Luo; Hengjiang Cong; Jing Zhang; Tianyou Peng

    2017-01-01

    [RuCl(L1)(MeCN) 2 ]Cl (1) and [RuCl(L2)(MeCN) 2 ]Cl (2) complexes were prepared through the reaction of [RuCl2(p-cymene)] 2 with 2,6-bis(benzimidazole-2-yl)-4-hydroxy-pyridine (L1) or 2,6-bis(benzimidazole- 2-yl) pyridine (L2) in acetonitrile, respectively. The treatment of [Ru(OTf)(L2)(MeCN) 2 ]OTf (3) with 1 equivalent of PPh 3 in ethanol resulted in the formation of [Ru(L2 -1 )(MeCN)(PPh 3 ) 2 ]OTf (4), in which one of the N-H moieties of L2 is deprotonated to give an anionic ligand (L2 -1 ). It was found that complex 1 can catalyze the hydrogenation of CO 2 to formate salts, producing sodium formate in 34.0% yield with a turnover number (TON) of 407 under the optimized conditions. Further investigations revealed that complexes 1-4 can efficiently catalyze the hydrogenation of sodium bicarbonate to sodium formate, and the catalytic activity follows the order 4 ≥ 1 ≥ 2 ≅ 3. In particular, sodium formate was obtained in good yield (77%) with a high TON (1530) when complex 4 was used as the catalyst. The present results illustrate a new example of Ru(II) complexes bearing a rigid N'NN' framework for the efficient hydrogenation of CO 2 to formate salts in a homogeneous system. (authors)

  15. Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M.

    1943-02-19

    A transcript is presented of a speech on the history of the development of hydrogenation of coal and tar. Apparently the talk had been accompanied by the showing of photographic slides, but none of the pictures were included with the report. In giving the history, Dr. Pier mentioned the dependence of much of the development of hydrogenation upon previous development in the related areas of ammonia and methanol syntheses, but he also pointed out several ways in which equipment appropriate for hydrogenation differed considerably from that used for ammonia and methanol. Dr. Pier discussed the difficulties encountered with residue processing, design of the reaction ovens, manufacture of ovens and preheaters, heating of reaction mixtures, development of steels, and development of compressor pumps. He described in some detail his own involvement in the development of the process. In addition, he discussed the development of methods of testing gasolines and other fuels. Also he listed some important byproducts of hydrogenation, such as phenols and polycyclic aromatics, and he discussed the formation of iso-octane fuel from the butanes arising from hydrogenation. In connection with several kinds of equipment used in hydrogenation (whose pictures were being shown), Dr. Pier gave some of the design and operating data.

  16. Hydrogenation of unactivated enamines to tertiary amines: rhodium complexes of fluorinated phosphines give marked improvements in catalytic activity

    Directory of Open Access Journals (Sweden)

    Sergey Tin

    2015-05-01

    Full Text Available In the hydrogenation of sluggish unactivated enamine substrates, Rh complexes of electron-deficient phosphines are demonstrated to be far more reactive catalysts than those derived from triphenylphosphine. These operate at low catalyst loadings (down to 0.01 mol % and are able to reduce tetrasubstituted enamines. The use of the sustainable and environmentally benign solvent (R-limonene for the reaction is also reported with the amine isolated by acid extraction.

  17. Synthesis of zirconia-immobilized copper chelates for catalytic decomposition of hydrogen peroxide and the oxidation of polycyclic aromatic hydrocarbons

    Czech Academy of Sciences Publication Activity Database

    Baldrian, Petr; Merhautová, Věra; Cajthaml, Tomáš; Nerud, František; Stopka, Pavel; Gorbacheva, O.; Hrubý, Martin; Beneš, Milan J.

    2008-01-01

    Roč. 72, č. 11 (2008), s. 1721-1726 ISSN 0045-6535 R&D Projects: GA AV ČR IBS5020306 Institutional research plan: CEZ:AV0Z50200510; CEZ:AV0Z40320502; CEZ:AV0Z40500505 Keywords : degradation * polycyclic aromatic hydrocarbons * hydrogen peroxide Subject RIV: EE - Microbiology, Virology Impact factor: 3.054, year: 2008

  18. Modeling Hydrogen Generation Rates in the Hanford Waste Treatment and Immobilization Plant

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, Donald M.; Bryan, Samuel A.; Hallen, Richard T.; Sherwood, David J.; Stock, Leon M.

    2004-03-29

    This presentation describes a project in which Hanford Site and Environmental Management Science Program investigators addressed issues concerning hydrogen generation rates in the Hanford waste treatment and immobilization plant. The hydrogen generation rates of radioactive wastes must be estimated to provide for safe operations. While an existing model satisfactorily predicts rates for quiescent wastes in Hanford underground storage tanks, pretreatment operations will alter the conditions and chemical composition of these wastes. Review of the treatment process flowsheet identified specific issues requiring study to ascertain whether the model would provide conservative values for waste streams in the plant. These include effects of adding hydroxide ion, alpha radiolysis, saturation with air (oxygen) from pulse-jet mixing, treatment with potassium permanganate, organic compounds from degraded ion exchange resins and addition of glass-former chemicals. The effects were systematically investigated through literature review, technical analyses and experimental work.

  19. Hydrogen generation in SRAT with nitric acid and late washing flowsheets

    International Nuclear Information System (INIS)

    Hsu, C.W.

    1992-01-01

    Recently, SRTC recommended two process changes: (1) a final wash of the tetraphenylborate precipitate feed slurry and (2) the use of nitric acid to neutralize the sludge in the SRAT. The first change produced an aqueous hydrolysis product (PHA) with higher formic acid/formate and copper concentration, and reduced the nitrate content in the PHA by an order of magnitude. The second change is to substitute part of formic acid added to the SRAT with nitric acid, and therefore may reduce the hydrogen generated in the SRAT as well as provide nitrate as an oxidant to balance the redox state of the melter feed. The purpose of this report is to determine the pertinent variables that could affect the hydrogen generation rate with these process changes

  20. Towards numerical simulation of turbulent hydrogen combustion based on flamelet generated manifolds in OpenFOAM

    Science.gov (United States)

    Fancello, A.; Bastiaans, R. J. M.; de Goey, L. P. H.

    2013-10-01

    This work proposes an application of the Flamelet-Generated Manifolds (FGM) technique in the OpenFOAM environment. FGM is a chemical reduced method for combustion modeling. This technique treats the combustion process as the solution of a small amount of controlling variables. Regarding laminar simulation, a progress variable and enthalpy evolution can describe satisfactorily the problem. From a turbulent point of view, FGM can be applied to LES and RANS simulations, where the subgrid chemical terms are described with a β - PDF approach. These approaches apply satisfactorily in relatively simple gases, nevertheless for hydrogen are not more valid, due to preferential diffusion effects and instability of the flame structure. The overall aim of this research is to find technical solution for hydrogen gas turbines design in the next generation of Integrated Gasification Combined Cycle (IGCC) plants.