WorldWideScience

Sample records for reaction coal hydrogenation

  1. Alternative reaction routes during coal hydrogenation and coal derived oil upgrading

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, H.; Kordokuzis, G.; Langner, M. (University of Karlsruhe, Karlsruhe (Germany, F.R.). Engler-Bunte-Institute)

    1989-10-01

    Alternative reaction routes have been traced for the hydrodenitrogenation and hydrodeoxygenation of coal structure related model compounds. Reaction pathways are very structure specific. It is shown how reaction mechanisms switch from one route to another with changes in reaction conditions and catalyst features. Optimization of coal liquefaction processes can make use of this detailed understanding of selectivity. 5 refs., 7 figs.

  2. Process for hydrogenating coal and coal solvents

    Energy Technology Data Exchange (ETDEWEB)

    Shridharani, K.G.; Tarrer, A.R.

    1983-02-15

    A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260/sup 0/ C to 315/sup 0/ C in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent. Optimally, the reaction temperature is 275/sup 0/ C. Alternately, the reaction can be conducted in a hydrogen atmosphere at 350/sup 0/ C.

  3. Process for hydrogenating coal and coal solvents

    Science.gov (United States)

    Tarrer, Arthur R.; Shridharani, Ketan G.

    1983-01-01

    A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260.degree. C. to 315.degree. C. in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent. Optimally, the reaction temperature is 275.degree. C. Alternately, the reaction can be conducted in a hydrogen atmosphere at 350.degree. C.

  4. Coal reactions during shock heating in a hydrogen atmosphere. Reaktionsverhalten von Kohlen bei schockartiger Aufheizung in Wasserstoffatmosphaere

    Energy Technology Data Exchange (ETDEWEB)

    Sperling, R

    1987-04-30

    The study deals with the hydropyrolysis of coal under shock heating in order to learn more about the elementary reactions, which take place on the coal surface or in the interior of the carbon grain and which determine the product range and product yield. For recording the factors influencing primary cracking of products and the secondary reactions of the crack products, investigations were carried out by varying the particle diameter of the coals used (3 coals of different carbonization degrees) and the hydrogen pressure. For further recording of secondary reactions and thus the mechanism of the hydropyrolysis, typical crack products with primary character were presented on or in the coal; this was done by the absorption of a defined quantity of model compounds from the gas phase. For shock heating, the Curie point method (inductive heating) was used. It turned out that, with increasing H/sub 2/ pressure, the formation of H-transporting compounds and the availability of the molecular hydrogen from the gas phase is increased but the volatility of the reaction products is inhibited by cross-linking reactions of radicals with high-molecular crack products. High temperatures in shock heating can compensate this negative effect.

  5. Bond cleavage reactions of the bridge structure in coal in the presence of hydrogen donating compounds; Suiso kyoyosei kagobutsu sonzaika deno sekitanchu no kakyo kozo no kairetsu hanno

    Energy Technology Data Exchange (ETDEWEB)

    Bando, N.; Kidena, K.; Murata, S.; Nomura, M. [Osaka University, Osaka (Japan). Faculty of Engineering

    1996-10-28

    In this paper, bond cleavage reactions are discussed in relation to the softening and solubilization of coal. Were used 9,10-dihydroanthracene (DHA) and 9,10-dihydrophenanthrene (DHP) as models of hydrogen donating compounds in coal, and bibenzyl, 1,2-diethane, benzylphenylether, and 1,5-dibenzylnaphthalene were used as models of bridge structure compounds. They were compared mutually, as to reactivity of coal against DHA and DHP. For the homolytic cleavage of bridges, DHA with excellent radical supplement performance provided excellent hydrogen donating performance. While, for the ipso-position cleavage of bridges, it was found that DHP can act as an effective hydrogen donor. For the reaction between coal and hydrogenated aromatic compounds, cleavage of relatively weak bonds, such as ether linkage and dimethylene linkage, occurred at about 380{degree}C, and hydrogen from DHA or DHP was consumed. On the other hand, the results suggested that the cleavage reaction at ipso-position affected by hydrogen donating solvent is also important at temperature range around 420{degree}C. 2 refs., 3 figs., 1 tab.

  6. Reaction of methane with coal

    Energy Technology Data Exchange (ETDEWEB)

    Yang, K.; Batts, B.D.; Wilson, M.A.; Gorbaty, M.L.; Maa, P.S.; Long, M.A.; He, S.J.X.; Attala, M.I. [Macquarie University, Macquarie, NSW (Australia). School of Chemistry

    1997-10-01

    A study of the reactivities of Australian coals and one American coal with methane or methane-hydrogen mixtures, in the range 350-400{degree}C and a range of pressures (6.0-8.3 MPa, cold) is reported. The effects of aluminophosphates (AIPO) or zeolite catalysts, with and without exchanged metals, on reactivity have also been examined. Yields of dichloromethane extractable material are increased by using a methane rather than a nitrogen atmosphere and different catalysts assist dissolution to various extends. It appears that surface exchanged catalysts are effective, but incorporating metals during AIPO lattice formation is detrimental. Aluminium phosphate catalysts are unstable to water produced during coal conversion, but are still able to increase extraction yields. For the American coal, under methane-hydrogen and a copper exchanged zeolite, 51.5% conversion was obtained, with a product selectivity close to that obtained under hydrogen alone, and with only 2% hydrogen consumption. The conversion under methane-hydrogen was also to that obtained under hydrogen alone, while a linear dependence of conversion on proportion of methane would predict a 43% conversion under methane-hydrogen. This illustrates a synergistic effect of the methane-hydrogen atmosphere for coal liquefaction using this catalyst systems. 31 refs., 5 figs., 7 tabs.

  7. Two-stage coal liquefaction without gas-phase hydrogen

    Science.gov (United States)

    Stephens, H.P.

    1986-06-05

    A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

  8. Hydrogen evolution reaction catalyst

    Science.gov (United States)

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  9. Alcohols as hydrogen-donor solvents for treatment of coal

    Science.gov (United States)

    Ross, David S.; Blessing, James E.

    1981-01-01

    A method for the hydroconversion of coal by solvent treatment at elevated temperatures and pressure wherein an alcohol having an .alpha.-hydrogen atom, particularly a secondary alcohol such as isopropanol, is utilized as a hydrogen donor solvent. In a particular embodiment, a base capable of providing a catalytically effective amount of the corresponding alcoholate anion under the solvent treatment conditions is added to catalyze the alcohol-coal reaction.

  10. Basic studies on coal liquefaction reaction, reforming and utilization of liquefaction products

    Energy Technology Data Exchange (ETDEWEB)

    Shiraishi, M. (National Institute for Resources and Environment, Tsukuba (Japan))

    1993-09-01

    This report describes the achievement of research and development of coal liquefaction technologies in the Sunshine Project for FY 1992, regarding the coal liquefaction reaction, reforming and utilization of liquefaction products. For the fundamental study on coal liquefaction reaction, were investigated effect of asphaltene in petroleum residue on coprocessing, pretreatment effect in coprocessing of Taiheiyo coal and tarsand bitumen using oil soluble catalyst, solubilization and liquefaction of Taiheiyo coal at mild conditions with the aid of super acid, and flash hydropyrolysis of finely pulverized swollen coal under high hydrogen pressure. On the other hand, for the study on hydrotreatment of coal derived liquid, were investigated catalytic hydroprocessing of Wandoan coal liquids, production of gasoline from coal liquids by fluid catalytic cracking, solvent extraction of phenolic compounds from coal liquids, and separation of hetero compounds in coal liquid by means of high pressure crystallization. Further progress in these studies has been confirmed. 9 figs., 6 tabs.

  11. Study on hydrogen transfer in coal liquefaction by tritium and carbon-14 tracers

    International Nuclear Information System (INIS)

    Nitoh, Osamu; Kabe, Toshiaki; Kabe, Yaeko.

    1985-01-01

    For the analysis of mechanism of hydrogenation and cracking of coal, the liquefaction of Taiheiyo coal using tritium labeled gaseous hydrogen and tritium labeled tetralin with small amounts of carbon-14 labeled naphthalene has been studied. Taiheiyo coal(25g) was thermally decomposed in tetralin or naphthalene solvent(75g) at 400--440 0 C under the initial hydrogen pressure of 5.9MPa for 30min with Ni-Mo-Al 2 O 3 catalyst(0--5g). The reaction mixture in an autoclave was separated by filtration, distillation and solvent extraction. Produced gas, oils and the solvent were analyzed by gas chromatography. The tritium and carbon-14 contents of separated reaction products were measured with a liquid scintilation counter to study the hydrogen transfer mechanism. The distribution of reaction products and the amount of hydrogen transfer from gas or solvent to the products were also determined. In hydrogen donor solvent such as tetralin, the coal liquefaction yield was independent from the catalyst, but the catalyst was effective in hydrocracking of preasphaltene and asphaltene. In naphthalene solvent, the coal liquefaction reaction hardly occured in the absence of the catalyst, because hydrogen transfer from both the solvent and gaseous hydrogen was scarce. Tritium distribution in the reaction products showed that complicated hydrogen exchange reactions between gaseous hydrogen, coal liquids and solvent came out by the presence of coal liquids and catalyst. The very small amounts of carbon-14 transferred to the liquefaction products showed that carbon exchange or transfer between solvent and coal did not take place. (author)

  12. Coal pyrolysis under hydrogen-rich gases

    Energy Technology Data Exchange (ETDEWEB)

    Liao, H.; Sun, C.; Li, B.; Liu, Z. [Chinese Academy of Sciences, Taiyuan (China). State Key Laboratory of Coal Conversion, Institute of Coal Chemistry

    1998-04-01

    To improve the economy of the pyrolysis process by reducing the hydrogen cost, it is suggested to use cheaper hydrogen-rich gases such as coke-oven gas (COG) or synthesis gas (SG) instead of pure hydrogen. The pyrolysis of Chinese Xianfeng lignite which was carried out with real COG and SG at 3-5 MPa, a final temperature of 650{degree}C and a heating rate of 5{degree}C/min in a 10g fixed-bed reactor is compared with coal pyrolysis with pure hydrogen and nitrogen under the same conditions. The results indicate that compared with hydropyrolysis at the same total pressure, the total conversion and tar yields from coal pyrolysis with COG and SG decreases while the unwanted water increases. However, at the same H{sub 2} partial pressure, the tar yields and yields of BBTX, PCX and naphthalene from the pyrolysis of coal with COG and SG are all significantly higher than those of hydropyrolysis. Therefore, it is possible to use COG and SG instead of pure hydrogen. 8 refs., 3 figs., 6 tabs.

  13. Novel technique for coal pyrolysis and hydrogenation production analysis

    Energy Technology Data Exchange (ETDEWEB)

    Pfefferle, L.D.

    1990-01-01

    The overall objective of this study is to establish vacuum ultraviolet photoionization-MS and VUV pulsed EI-MS as useful tools for a simpler and more accurate direct mass spectrometric measurement of a broad range of hydrocarbon compounds in complex mixtures for ultimate application to the study of the kinetics of coal hydrogenation and pyrolysis processes. The VUV-MS technique allows ionization of a broad range of species with minimal fragmentation. Many compounds of interest can be detected with the 118 nm wavelength, but additional compound selectivity is achievable by tuning the wavelength of the photo-ionization source in the VUV. Resonant four wave mixing techniques in Hg vapor will allow near continuous tuning from about 126 to 106 nm. This technique would facilitate the scientific investigation of coal upgrading processes such as pyrolysis and hydrogenation by allowing accurate direct analysis of both stable and intermediate reaction products.

  14. Mineral catalysis of oil producing reactions in coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Shridharani, K.G.

    1983-01-01

    This work was concerned primarily with the development of a relatively inexpensive, readily available, high activity catalyst that can be used as a disposable catalyst in coal liquefaction processes. For a fair evaluation of the developmental mineral catalyst (presulfided iron oxide), it was necessary to determine at different stages of this work, whether catalyst inhibition, deactivation or activity was the limiting factor in coal liquefaction catalysis. First, different routes were explored to prepare a high hydrogenation activity, iron-based catalyst. Naphthalene hydrogenation was used as a model reaction to rate the hydrogenation activities of different additives. Presulfiding of iron oxide with H/sub 2/S, under controlled conditions, rendered the highest hydrogenation activity mineral catalyst, which had a hydrogenation activity even greater than that of commercial CoMo/Al/sub 2/O/sub 3/ catalyst sulfided with creosote oil and hydrogen. Sulfiding of CoMo/Al/sub 2/O/sub 3/ catalyst with H/sub 2/S remarkably improved its initial hydrogenation activity. Second, the catalyst inhibition and deactivation during liquefaction were studied. Liquefaction-process solvents contain a number of compounds that can either deactivate or inhibit the hydrogenation activity of a catalyst. Finally, the hydrocracking activity of the presulfided iron oxide catalyst was compared with that of commercial catalysts, CoMo/Al/sub 2/O/sub 3/ and low alumina FCC catalyst.

  15. Advanced Hydrogen Transport Membrane for Coal Gasification

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Joseph [Praxair, Inc., Tonawanda, NY (United States); Porter, Jason [Colorado School of Mines, Golden, CO (United States); Patki, Neil [Colorado School of Mines, Golden, CO (United States); Kelley, Madison [Colorado School of Mines, Golden, CO (United States); Stanislowski, Josh [Univ. of North Dakota, Grand Forks, ND (United States); Tolbert, Scott [Univ. of North Dakota, Grand Forks, ND (United States); Way, J. Douglas [Colorado School of Mines, Golden, CO (United States); Makuch, David [Praxair, Inc., Tonawanda, NY (United States)

    2015-12-23

    A pilot-scale hydrogen transport membrane (HTM) separator was built that incorporated 98 membranes that were each 24 inches long. This separator used an advanced design to minimize the impact of concentration polarization and separated over 1000 scfh of hydrogen from a hydrogen-nitrogen feed of 5000 scfh that contained 30% hydrogen. This mixture was chosen because it was representative of the hydrogen concentration expected in coal gasification. When tested with an operating gasifier, the hydrogen concentration was lower and contaminants in the syngas adversely impacted membrane performance. All 98 membranes survived the test, but flux was lower than expected. Improved ceramic substrates were produced that have small surface pores to enable membrane production and large pores in the bulk of the substrate to allow high flux. Pd-Au was chosen as the membrane alloy because of its resistance to sulfur contamination and good flux. Processes were developed to produce a large quantity of long membranes for use in the demonstration test.

  16. Composition of hydrogenation products of Borodino brown coal

    Energy Technology Data Exchange (ETDEWEB)

    M.A. Gyul' malieva; A.S. Maloletnev; G.A. Kalabin; A.M. Gyul' maliev [Institute for Fossil Fuels, Moscow (Russian Federation)

    2008-02-15

    The composition of liquid products of hydrogenation of brown coal from the Borodino deposit was determined by means of {sup 13}C NMR spectroscopy and chemical thermodynamics methods. It was shown that the group composition of the liquid hydrogenation products at thermodynamic equilibrium is predictable from the elemental composition of the organic matter of parent coal. 9 refs., 5 figs., 6 tabs.

  17. Intermolecula transfer and elimination of molecular hydrogen in thermal reactions of unsaturated organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Suria, Sabartanty [Iowa State Univ., Ames, IA (United States)

    1995-02-10

    Two reactions which are important to coal liquefaction include intermolecular transfer and the elimination of two hydrogen atoms. We have designed several model reactions to probe the viability of several hydrogen transfer and elimination pathways. This report described studies on these reactions using organic model compounds.

  18. Coal/Polymer Coprocessing with Efficient Use of Hydrogen.

    Energy Technology Data Exchange (ETDEWEB)

    Broadbelt, L.J.

    1997-08-31

    The objective of the current research is to investigate the feasibility of coprocessing coal with waste polymers, with particular interest in employing the polymers as an alternate hydrogen source for coal upgrading and simultaneously recovering high valued fuels and chemicals from plastic waste. A chemical modeling approach was employed in which real and model feedstocks were used to identify the underlying reaction pathways, kinetics, and mechanisms controlling coal liquefaction in the presence of plastics and catalysts. Simple model systems were employed to facilitate product analysis and obtain information about the intrinsic reactivity. When reacted in binary mixtures, the conversion of tetradecane, a model compound of polyethylene, increased while the selectivities to primary products of 4-(naphthylmethyl) bibenzyl were enhanced. Experiments in the last six months in which the relative concentrations of the components were varied revealed that the effect was indeed a chemical one and not simply a result of dilution. An experimental protocol was developed to conduct experiments at elevated pressures more representative of coal liquefaction conditions. Preliminary experiments with real feedstocks allowed the extrinsic factors (i.e., diffusion limitations, solvent effects) to be identified. The combination of these two sets of experiments will ultimately be used to carry out process optimization and formulate strategies for catalyst development.

  19. FY 1980 Report on results of Sunshine Project. Research and development of coal liquefaction techniques (Development of direct hydrogenation type liquefaction plant and researches on liquefaction reactions in the presence of iron-based catalyst); 1980 nendo sekitan ekika gijutsu no kenkyu kaihatsu, chokusetsu suiten ekika plant no kaihatsu seika hokokusho. Tetsukei shokubai ni yoru ekika hanno no kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1981-03-01

    This program is aimed at development of iron-based catalyst suited for direct hydrogenation type coal liquefaction by elucidating the effects of the catalyst on the liquefaction reactions. The iron-based catalyst seems to act as the radical stabilizer rather than the reaction promoter, because the increased quantity of the catalyst and increased H{sub 2} pressure share the common pattern rather than the catalyst enhances the activity, which is associated with increased reaction temperature or residence time. This is more notably observed when the coal species is changed to brown coal. In other words, recombination of the decomposition products by polycondensation is accelerated in the presence of the catalyst in decomposition of brown coal from bituminous coal, with the result that the catalyst effects are more notably observed. Whether this results from difference in age between brown coal and bituminous coal or content of specific types of ashes should be elucidated, because this point is considered to deeply relate to eventual development of the liquefaction reaction system. The FY 1980 program includes the primary screening of different types of iron compounds and tests of some iron-metal-based catalysts. (NEDO)

  20. Reaction of hydrogen atoms with acrylaldehyde

    International Nuclear Information System (INIS)

    Koda, Seiichiro; Nakamura, Kazumoto; Hoshino, Takashi; Hikita, Tsutomu

    1978-01-01

    The reaction of hydrogen atoms with acrylaldehyde was investigated in a fast flow reactor equipped with a time-of-flight type mass spectrometer under reduced pressure. Main reaction products were carbon monoxide, ethylene, ethane, methane, and propanal. Consideration of the distributions of the reaction products under various reaction conditions showed that hydrogen atoms attacked the C=C double bond, especially its inner carbon side under reduced pressure. Resulting hot radicals caused subsequent reactions. The relative value of the apparent bimolecular rate constant of the reaction against that of trans-2-butene with hydrogen atoms was 1.6+-0.2, which supported the above-mentioned initial reaction. (auth.)

  1. Hydrogen production from coal using a nuclear heat source

    Science.gov (United States)

    Quade, R. N.

    1976-01-01

    A strong candidate for hydrogen production in the intermediate time frame of 1985 to 1995 is a coal-based process using a high-temperature gas-cooled reactor (HTGR) as a heat source. Expected process efficiencies in the range of 60 to 70% are considerably higher than all other hydrogen production processes except steam reforming of a natural gas. The process involves the preparation of a coal liquid, hydrogasification of that liquid, and steam reforming of the resulting gaseous or light liquid product. A study showing process efficiency and cost of hydrogen vs nuclear reactor core outlet temperature has been completed, and shows diminishing returns at process temperatures above about 1500 F. A possible scenario combining the relatively abundant and low-cost Western coal deposits with the Gulf Coast hydrogen users is presented which provides high-energy density transportation utilizing coal liquids and uranium.

  2. Solubilities of hydrogen and methane in coal liquids

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Ho-mu; Sebastian, H M; Simnick, J J; Chao, Kwang Chu

    1981-04-01

    The solubilities of hydrogen and methane in Exxon Donor Solvent (EDS) and Solvent Refined Coal II (SRC-II) coal liquids are determined at 190 and 270 C and pressures to 250 atm. Two narrow boiling distillate cuts from EDS and three from SRC-II are studied.

  3. Non-catalytic transfer hydrogenation in supercritical CO2 for coal liquefaction

    Science.gov (United States)

    Elhussien, Hussien

    This thesis presents the results of the investigation on developing and evaluating a low temperature (coal dissolution in supercritical CO2. The main idea behind the thesis was that one hydrogen atom from water and one hydrogen atom from the hydrogen transfer agent (HTA) were used to hydrogenate the coal. The products of coal dissolution were non-polar and polar while the supercritical CO2, which enhanced the rates of hydrogenation and dissolution of the non-polar molecules and removal from the reaction site, was non-polar. The polar modifier (PM) for CO2 was added to the freed to aid in the dissolution and removal of the polar components. The addition of a phase transfer agent (PTA) allowed a seamless transport of the ions and by-product between the aqueous and organic phases. DDAB, used as the PTA, is an effective phase transfer catalyst and showed enhancement to the coal dissolution process. COAL + DH- +H 2O → COAL.H2 + DHO-- This process has a great feature due to the fact that the chemicals were obtained without requir-ing to first convert coal to CO and H2 units as in indirect coal liquefaction. The experiments were conducted in a unique reactor set up that can be connected through two lines. one line to feed the reactor with supercritical CO 2 and the other connected to gas chromatograph. The use of the supercritical CO2 enhanced the solvent option due to the chemical extraction, in addition to the low environmental impact and energy cost. In this thesis the experiment were conducted at five different temperatures from atmos-pheric to 140°C, 3000 - 6000 psi with five component of feed mixture, namely water, HTA, PTA, coal, and PM in semi batch vessels reactor system with a volume of 100 mL. The results show that the chemicals were obtained without requiring to first convert coal to CO and H2 units as in indirect coal liquefaction. The results show that the conversion was found to be 91.8% at opti-mum feed mixtures values of 3, 1.0 and 5.4 for water: PM

  4. Effect of hydrogen chloride on the corrosion of an FeCrAlY alloy in simulated coal gasifier atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Coley, K.S.; Rhoades-Brown, J.E.; Blick, K.

    1989-03-01

    An iron chromium aluminium yttrium steel was exposed to a simulated coal gasifier atmosphere containing 1000 ppm and 2200 ppm hydrogen chloride at 450/sup 0/C. Increasing hydrogen chloride content was found to accelerate reaction rates, and significantly alter the microstructure and composition of the corrosion product. Tentative explanations for these results, involving vapour phase transport of metal chlorides are proposed.

  5. Report on the Sunshine Project in fiscal 1988 in research of coal liquefying technologies. Studies on direct hydrogenation liquefying reaction mechanism and prevention of carbonization; 1989 nendo sekitan no ekika gijutsu ni kansuru kenkyu hokokusho. Chokusetsu suiten ekika hanno kiko to tanka boshi no kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1989-07-01

    This paper reports the research of coal liquefying technologies in the Sunshine Project in fiscal 1988. The research was performed with importance placed on the fundamentals of coal liquefaction and high value added compounds. Production of n-paraffin in the liquefying reaction occurs from reduction of acidic ester, and this ester structure contributes to cross-linking of aromatic rings. Most of the aromatic rings in coal has long side chains. A hypothesis was assumed that these chains have been produced from reaction of lignin in plants with fatty acid or alcohol. The hypothesis was verified from a synthesizing reaction by model substances. This could be said an initial reaction model for coalification. In order to verify de-alkylating reaction of the liquefied oil, model substances were used to investigate the products. Benzene having long alkyl side chains have the alkyl group dissociated, and on the other hand cyclization progressed producing naphthalene. Melting performance during coking is attributed to a great amount of solvent soluble low molecular constituents contained in coal. These constituents are contained in close contact in a net-like structure, which is loosened only by heating extraction, and extracted. They have no hydrogen donating performance. (NEDO)

  6. Carbon-free hydrogen production from low rank coal

    Science.gov (United States)

    Aziz, Muhammad; Oda, Takuya; Kashiwagi, Takao

    2018-02-01

    Novel carbon-free integrated system of hydrogen production and storage from low rank coal is proposed and evaluated. To measure the optimum energy efficiency, two different systems employing different chemical looping technologies are modeled. The first integrated system consists of coal drying, gasification, syngas chemical looping, and hydrogenation. On the other hand, the second system combines coal drying, coal direct chemical looping, and hydrogenation. In addition, in order to cover the consumed electricity and recover the energy, combined cycle is adopted as addition module for power generation. The objective of the study is to find the best system having the highest performance in terms of total energy efficiency, including hydrogen production efficiency and power generation efficiency. To achieve a thorough energy/heat circulation throughout each module and the whole integrated system, enhanced process integration technology is employed. It basically incorporates two core basic technologies: exergy recovery and process integration. Several operating parameters including target moisture content in drying module, operating pressure in chemical looping module, are observed in terms of their influence to energy efficiency. From process modeling and calculation, two integrated systems can realize high total energy efficiency, higher than 60%. However, the system employing coal direct chemical looping represents higher energy efficiency, including hydrogen production and power generation, which is about 83%. In addition, optimum target moisture content in drying and operating pressure in chemical looping also have been defined.

  7. Report of National Research Institute for Pollution and Resources for fiscal 1979. Research on conversion of coal to petroleum, research on coal liquefaction, high pressure liquid phase hydrogenation of coal by continuous test equipment, and manufacture of coal chemicals; 1979 nendo sekitan no yuka no kenkyu / sekitan no ekika no kenkyu / renzoku shiken sochi ni yoru sekitan no koatsu ekiso suisoka bunkai / coal chemicals no seizo

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1980-07-01

    Research was conducted on conversion of coal to petroleum for the purpose of securing substitute liquid fuel. Recovery of hydrogen from the waste gas from the conversion process was explained, as were the conversion results from various coals produced in Japan. In coal liquefaction researches with the aim of manufacturing artificial petroleum, a report was made on each of the researches, i.e., the experiment results of coal liquefaction using various catalysts, manufacture of hydrogen by water gas reaction, catalytic action against coal paste, action of mixed oil and pressure against coal paste, result of hydrogen adding test for coal paste using an intermediate scale device, test result of secondary hydrogen addition for coal liquefied oil, and the test result of continuous secondary hydrogen addition for the liquefied oil. In the manufacture of fuel oil by hydro-cracking of coal or tar, a report was made on high pressure liquid phase hydrogenation of coal using a continuous testing device. Aromatic chemicals useful as chemical materials are supposed to be obtained by cutting inter-polymerized-unit bonding to make low molecules from the chemical structure of coal, removing surrounding radicals and simplifying it. A report was also made on the experiment of manufacturing coal chemicals by combination of high pressure liquid phase hydrogenation and hydro-dealkylation. (NEDO)

  8. Hydrogen production from coal using a nuclear heat source

    International Nuclear Information System (INIS)

    Quade, R.N.

    1977-01-01

    A strong candidate for hydrogen production in the intermediate time frame of 1990 to 1995 is a coal-based process using a high-temperature gas-cooled reactor (HTGR) as a heat source. Expected process efficiencies in the range of 60 to 70% are considerably higher than all other hydrogen production processes except steam reforming of a natural gas - a feedstock which may not be available in large quantities in this time frame. The process involves the preparation of a coal liquid, hydrogasification of that liquid, and steam reforming of the resulting gaseous or light liquid product. Bench-scale experimental work on the hydrogasification of coal liquids is being carried out. A study showing process efficiency and cost of hydrogen vs nuclear reactor core outlet temperature has been completed and shows diminishing returns at process temperatures above about 1500 0 F. (author)

  9. Ternary alloy nanocatalysts for hydrogen evolution reaction

    Indian Academy of Sciences (India)

    Generation of hydrogen through water splitting is an impor- tant area of research. ... Splitting of water using electricity makes this reaction feasible, but requires a catalyst to overcome .... The obtained product was dried in air and heated at 700.

  10. Possibility of obtaining hydrogen from coal/waste-tyre mixture

    Czech Academy of Sciences Publication Activity Database

    Kříž, Vlastimil; Brožová, Zuzana; Přibyl, Oldřich; Sýkorová, Ivana

    2008-01-01

    Roč. 89, č. 11 (2008), s. 1069-1075 ISSN 0378-3820 R&D Projects: GA ČR(CZ) GA105/07/1407 Institutional research plan: CEZ:AV0Z30460519 Keywords : hydrogen * coal * waste tyres Subject RIV: DD - Geochemistry Impact factor: 2.066, year: 2008 www.elsevier.com/locate/fuproc/

  11. Hydrogen Transfer during Liquefaction of Elbistan Lignite to Biomass; Total Reaction Transformation Approach

    Science.gov (United States)

    Koyunoglu, Cemil; Karaca, Hüseyin

    2017-12-01

    Given the high cost of the tetraline solvent commonly used in liquefaction, the use of manure with EL is an important factor when considering the high cost of using tetraline as a hydrogen transfer source. In addition, due to the another cost factor which is the catalyst prices, red mud (commonly used, produced as a byproduct in the production of aluminium) is reduced cost in the work of liquefaction of coal, biomass, even coal combined biomass, corresponding that making the EL liquefaction an agenda for our country is another important factor. Conditions for liquefaction experiments conducted for hydrogen transfer from manure to coal; Catalyst concentration of 9%, liquid/solid ratio of 3/1, reaction time of 60 min, fertilizer/lignite ratio of 1/3, and the reaction temperature of 400 °C, the stirred speed of 400 rpm and the initial nitrogen pressure of 20 bar was fixed. In order to demonstrate the hydrogen, transfer from manure to coal, coal is used solely, by using tetraline (also known as a hydrogen carrier) and distilled water which is not hydrogen donor as a solvent in the co-liquefaction of experiments, and also the liquefaction conditions are carried out under an inert (N2) gas atmosphere. According to the results of the obtained liquefaction test; using tetraline solvent the total liquid product conversion percentage of the oil + gas conversion was 38.3 %, however, the results of oil+gas conversion obtained using distilled water and EL combined with manure the total liquid product conversion percentage was 7.4 %. According to the results of calorific value and elemental analysis, only the ratio of (H/C)atomic of coal obtained by using tetraline increased with the liquefaction of manure and distilled water. The reason of the increase in the amount of hydrogen due to hydrogen transfer from the manure on the solid surface of the coal, and also on the surface of the inner pore of the coal during the liquefaction, brings about the evaluation of the coal as a

  12. The reaction of uranium with moist hydrogen

    International Nuclear Information System (INIS)

    Pearce, R.J.; Kay, P.

    1987-10-01

    The reaction of uranium in moist hydrogen at a total pressure of 101 kPa over the temperature range 105 0 -200 0 C and water vapour pressures in the range 5-100 kPa has been examined in a limited thermogravimetric study. It has been shown that initially there is a period during which only linear kinetics are observed with a rate similar to that exhibited in similarly moist argon, i.e. hydrogen has no apparent effect on the reaction. At water vapour pressures of and above 49 kPa, corresponding to hydrogen:water vapour pressure ratios in the range 1:1 to 1:100, over the exposure times studied (not > 20h) only such linear kinetics are observed. Below this water vapour pressure and after an initial period of linear kinetics a continuously increasing reaction rate was observed in some instances resulting from rapid attach on localised areas. The localised reaction rates were approximately 2-3 orders of magnitude faster than the original linear reaction kinetics and the interaction rates in either moist argon or moist air. Comparison with a single experiment carried out at 150 0 C indicated that breakaway rates were approaching that in dry hydrogen. During breakaway attack there was a significant increase in the relative amounts of uranium hydride formed. The duration of the linear kinetics phase was extended by pre-oxidation of the uranium surface, decreasing temperature at a constant water vapour pressure, or increasing water vapour pressure (or water vapour: hydrogen pressure ratio) at a constant temperature. (author)

  13. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  14. Technical project of complex fast cycle heat treatment of hydrogenous coal preparation

    OpenAIRE

    Moiseev, V. A.; Andrienko, V. G.; Pileckij, V. G.; Urvancev, A. I.; Gvozdyakov, Dmitry Vasilievich; Gubin, Vladimir Evgenievich; Matveev, Aleksandr Sergeevich; Savostiyanova, Ludmila Viktorovna

    2015-01-01

    Problems of heat-treated milled hydrogenous coal preparation site creation in leading fast cycle heat treatment complex were considered. Conditions for effective use of electrostatic methods of heat-treated milled hydrogenous coal preparation were set. Technical project of heat treatment of milled hydrogenous coal preparation site was developed including coupling of working equipment complex on fast heat treatment and experimental samples of equipment being designed for manufacturing. It was ...

  15. N-Alkylation by Hydrogen Autotransfer Reactions.

    Science.gov (United States)

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.

  16. Activity and selectivity of three molybdenum catalysts for coal liquefaction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W.; Pellegrino, J.L.

    The activity and selectivity of three different molybdenum catalysts for reactions occurring in coal liquefaction, specifically for hydrogenation (HYD), hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrocracking (HYC), have been examined. The three molybdenum catalysts used were molybdenum napthenate, molybdenum on ..gamma..-alumina, and a precipitated, disordered MoS/sub 2/. Molybdenum naphthenate was most selective for HYD and HDN. All three catalysts exhibited approximately equal activity for HDS and HDO and little selectivity for HYC of alkyl bridge structures. The activity and selectivity of the three molybdenum catalysts for producing hydrocarbons and removing heteroatoms from coal during liquefaction were determined and compared. Molybdenum naphthenate was the most active catalyst for hydrocarbon production and removal of nitrogen- and oxygen-containing species during coal liquefaction. 31 refs., 4 figs., 7 tabs.

  17. Chemical looping coal gasification with calcium ferrite and barium ferrite via solid–solid reactions

    International Nuclear Information System (INIS)

    Siriwardane, Ranjani; Riley, Jarrett; Tian, Hanjing; Richards, George

    2016-01-01

    Highlights: • BaFe 2 O 4 and CaFe 2 O 4 are excellent for chemical looping coal gasification. • BaFe 2 O 4 and CaFe 2 O 4 have minimal reactivity with synthesis gas. • Steam enhances the gasification process with these oxygen carriers. • Reaction rates of steam gasification of coal with CaFe 2 O 4 was better than with gaseous oxygen. • Coal gasification appears to be via solid–solid interaction with the oxygen carrier. - Abstract: Coal gasification to produce synthesis gas by chemical looping was investigated with two oxygen carriers, barium ferrite (BaFe 2 O 4 ) and calcium ferrite (CaFe 2 O 4 ). Thermo-gravimetric analysis (TGA) and fixed-bed flow reactor data indicated that a solid–solid interaction occurred between oxygen carriers and coal to produce synthesis gas. Both thermodynamic analysis and experimental data indicated that BaFe 2 O 4 and CaFe 2 O 4 have high reactivity with coal but have a low reactivity with synthesis gas, which makes them very attractive for the coal gasification process. Adding steam increased the production of hydrogen (H 2 ) and carbon monoxide (CO), but carbon dioxide (CO 2 ) remained low because these oxygen carriers have minimal reactivity with H 2 and CO. Therefore, the combined steam–oxygen carrier produced the highest quantity of synthesis gas. It appeared that neither the water–gas shift reaction nor the water splitting reaction promoted additional H 2 formation with the oxygen carriers when steam was present. Wyodak coal, which is a sub-bituminous coal, had the best gasification yield with oxygen carrier–steam while Illinois #6 coal had the lowest. The rate of gasification and selectivity for synthesis gas production was significantly higher when these oxygen carriers were present during steam gasification of coal. The rates and synthesis gas yields during the temperature ramps of coal–steam with oxygen carriers were better than with gaseous oxygen.

  18. Research on Improving Low Rank Coal Caking Ability by Moderate Hydrogenation

    Science.gov (United States)

    Huang, Peng

    2017-12-01

    The hydrogenation test of low metamorphic coal was carried out by using a continuous hydrogen reactor at the temperature of (350-400)°C and the initial hydrogen pressure of 3 ~ 6Mpa. The purpose of the experiment was to increase the caking property, and the heating time was controlled from 30 to 50min. The test results show that the mild hydrogenation test, no adhesion of low metamorphic coal can be transformed into a product having adhesion, oxygen elements in coal have good removal, the calorific value of the product has been improved significantly and coal particles during pyrolysis, swelling, catalyst, hydrogenation, structural changes and the combined effects of particles a new component formed between financial and is a major cause of coal caking enhancement and lithofacies change, coal blending test showed that the product can be used effectively in the coking industry.

  19. Kinetics of hydrogen isotope exchange reactions

    International Nuclear Information System (INIS)

    Gold, V.; McAdam, M.E.

    1975-01-01

    Under the influence of tritium β-radiation, 1,4-dioxan undergoes hydrogen exchange with the solvent water. The inhibition of the reaction by known electron scavengers (Ag + , Cu 2+ , Ni 2+ , Co 2+ , Zn 2+ , H 3 + O) and also by species with high reactivity towards hydroxyl radicals but negligible reactivity towards solvated electrons (N 3 - , Br - , SCN - ) has been examined in detail. γ-irradiation similarly induces hydrogen exchange. The action of scavengers is interpreted as requiring the involvement of two separately scavengeable primary radiolysis products in the sequence of reactions leading to exchange. The presence of electron scavengers, even at high concentration, does not totally inhibit the exchange, and a secondary exchange route, involving a low vacancy state of inhibitor cations, is considered responsible for the 'unscavengeable' portion of the reaction, by providing an alternative exchange route. Analogies are drawn between the exchange reaction and other radiation-induced reactions that are thought to involve spur processes. Some implication of radiation-chemical studies in water-alcohol mixtures are indicated. (author)

  20. Hydrogenolysis reactions characteristics of deashed coal under low temperature; Teionka ni okeru dakkai shoritan no suisoka bunkai hanno tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Owada, T.; Mashimo, K.; Wainai, T. [Nihon University, Tokyo (Japan). College of Science and Technology

    1996-10-28

    In relation to coal liquefaction, the effect of inorganic minerals on liquefaction reactivity and the effect of hydrofluoric acid (HF) treatment on organic molecular structure of coals were studied by demineralization of low-rank coals in HCl or HF solution. In experiment, Taiheiyo coal specimen was deashed in HCl solution at 25-70{degree}C for 6 hours while agitating, and in addition, deashed in HF solution. Hydrogenolysis of the deashed coal specimen was conducted using tetralin or methylnaphthalene as solvent under initial hydrogen pressure of 1.96MPa at reaction temperature of 693K for 60min. The experimental results are as follows. The ash content of Taiheiyo coal hardly offers catalysis in hydrogenolysis reaction. Carboxyl group increases in demineralization of coal because of breakage of bridged bonds. Organic structure of coal changes by demineralization in dense HF solution. Change in organic structure of coal by demineralization in dense HF solution is dependent on treatment temperature. 2 refs., 4 figs., 1 tab.

  1. Manufacture of aromatic hydrocarbons from coal hydrogenation products

    Energy Technology Data Exchange (ETDEWEB)

    A.S. Maloletnev; M.A. Gyul' malieva [Institute for Fossil Fuels, Moscow (Russian Federation)

    2007-08-15

    The manufacture of aromatic hydrocarbons from coal distillates was experimentally studied. A flow chart for the production of benzene, ethylbenzene, toluene, and xylenes was designed, which comprised the hydrogen treatment of the total wide-cut (or preliminarily dephenolized) fraction with FBP 425{sup o}C; fractional distillation of the hydrotreated products into IBP-60, 60-180, 180-300, and 300-425{sup o}C fractions; the hydro-cracking of middle fractions for increasing the yield of gasoline fractions whenever necessary; the catalytic reform of the fractions with bp up to 180{sup o}C; and the extraction of aromatic hydrocarbons.

  2. Hydrogen abstraction reactions by amide electron adducts

    International Nuclear Information System (INIS)

    Sevilla, M.D.; Sevilla, C.L.; Swarts, S.

    1982-01-01

    Electron reactions with a number of peptide model compounds (amides and N-acetylamino acids) in aqueous glasses at low temperature have been investigated using ESR spectroscopy. The radicals produced by electron attachment to amides, RC(OD)NDR', are found to act as hydrogen abstracting agents. For example, the propionamide electron adduct is found to abstract from its parent propionamide. Electron adducts of other amides investigated show similar behavior except for acetamide electron adduct which does not abstract from its parent compound, but does abstract from other amides. The tendency toward abstraction for amide electron adducts are compared to electron adducts of several carboxylic acids, ketones, aldehydes and esters. The comparison suggests the hydrogen abstraction tendency of the various deuterated electron adducts (DEAs) to be in the following order: aldehyde DEA > acid DEA = approximately ester DEA > ketone DEA > amide DEA. In basic glasses the hydrogen abstraction ability of the amide electron adducts is maintained until the concentration of base is increased sufficiently to convert the DEA to its anionic form, RC(O - )ND 2 . In this form the hydrogen abstracting ability of the radical is greatly diminished. Similar results were found for the ester and carboxylic acid DEA's tested. (author)

  3. Red soil as a regenerable sorbent for high temperature removal of hydrogen sulfide from coal gas

    International Nuclear Information System (INIS)

    Ko, T.-H.; Chu Hsin; Lin, H.-P.; Peng, C.-Y.

    2006-01-01

    In this study, hydrogen sulfide (H 2 S) was removed from coal gas by red soil under high temperature in a fixed-bed reactor. Red soil powders were collected from the northern, center and southern of Taiwan. They were characterized by XRPD, porosity analysis and DCB chemical analysis. Results show that the greater sulfur content of LP red soils is attributed to the higher free iron oxides and suitable sulfidation temperature is around 773 K. High temperature has a negative effect for use red soil as a desulfurization sorbent due to thermodynamic limitation in a reduction atmosphere. During 10 cycles of regeneration, after the first cycle the red soil remained stable with a breakthrough time between 31 and 36 min. Hydrogen adversely affects sulfidation reaction, whereas CO exhibits a positive effect due to a water-shift reaction. COS was formed during the sulfidation stage and this was attributed to the reaction of H 2 S and CO. Results of XRPD indicated that, hematite is the dominant active species in fresh red soil and iron sulfide (FeS) is a product of the reaction between hematite and hydrogen sulfide in red soils. The spinel phase FeAl 2 O 4 was found during regeneration, moreover, the amount of free iron oxides decreased after regeneration indicating the some of the free iron oxide formed a spinel phase, further reducting the overall desulfurization efficiency

  4. Reaction of dimethyl hydrogen phosphite with acecyclone

    International Nuclear Information System (INIS)

    Arbuzov, B.A.; Fuzhenkova, A.V.; Tyryshkin, N.I.

    1987-01-01

    In the presence of bases acecyclone reacts with dimethyl hydrogen phosphite with the formation of gamma-keto phosphonates with conjugated and unconjugated structures, and also an enol phosphate, a product containing a bond between oxygen of the cyclone and phosphorus. In the absence of bases, as well as the beta-keto phosphonate, gamma-keto phosphonates of cis and trans structure are formed; they are products of the 1,4 addition of dimethyl hydrogen phosphite to the conjugated fragment C=C-C=O of the cyclone. The compositions of the reaction mixture were determined by IR and NMR spectroscopy and TLC. Full-scale analysis of chemical shifts and spin-spin coupling constants was performed

  5. Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

    1996-10-28

    Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

  6. Reactions of oxygen containing structures in coal pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Hodek, W.; Kirschstein, J.; Van Heek, K.-H. (DMT-Gesellschaft fuer Forschung und Pruefung mbH, Essen (Germany, F.R.))

    1991-03-01

    In coal pyrolysis O-containing structures such as ether bridges and phenolic groups play an important role. Their reactions were studied by non-isothermal pyrolysis of a high volatile bituminous coal and some model polymers with gas chromatographic detection of the gaseous pyrolysis products. The coal was separated into the maceral groups vitrinite, exinite and inertinite, which showed markedly different pyrolysis behaviour. The formation of CO, methane and benzene was measured versus temperature. By comparison with polyphenyleneoxide and phenol-formaldehyde resins, it was found that the main volatilization, during which most of the tar is evolved, is initiated by cleavage of alkyl-aryl-ethers. Rearrangements of the primarily formed radicals lead to the formation of CO and methane at higher temperatures. 5 refs., 8 figs., 1 tab.

  7. Mechanism of obtaining carbon monoxide and hydrogen during brown coal radiolysis. [Gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Rustamov, V R; Kurbanov, M A; Dzantiev, B T; Kerimov, V K; Musaeva, P F

    1982-05-01

    This article analyzes effects of gamma radiation on the yield of products of coal gasification: hydrogen and carbon monoxide. Samples of brown coal from the Kansk-Achins basin were treated by gamma radiation with cobalt 60 radiation source. Analyses show that accumulation of hydrogen and carbon monoxide in brown coal under influence of gamma radiation is characterized by a constant rate. Yields of carbon monoxide and hydrogen amount to 0.16 molecule/100 electro volt and 0.21 molecule/electro volt respectively. Reducing radiation dose from 2.5 to 0.7 millirad/h reduces yields of hydrogen and carbon monoxide. Increasing temperature of vacuum brown coal pyrolysis from 200 to 600 C causes decrease of hydrogen yield. Hydrogen yield decrease during temperature increase is caused by a high content of aromatic nuclei in the samples used in the radiolysis. (5 refs.)

  8. Durable regenerable sorbent pellets for removal of hydrogen sulfide coal gas

    Science.gov (United States)

    Siriwardane, Ranjani V.

    1999-01-01

    Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form, usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

  9. Durable regenerable sorbent pellets for removal of hydrogen sulfide from coal gas

    Science.gov (United States)

    Siriwardane, Ranjani V.

    1997-01-01

    Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

  10. Effect of sulfur or hydrogen sulfide on initial stage of coal liquefaction in tetralin; Sekitan ekika shoki katei ni okeru io to ryuka suiso no hatasu yakuwari

    Energy Technology Data Exchange (ETDEWEB)

    Nakada, M. [Government Industrial Research Institute, Kyushu, Saga (Japan)

    1996-10-28

    It is well known that the solubilization of coal can be accelerated by adding sulfur or hydrogen sulfide during direct liquefaction of difficult coals. From the studies of authors on the coal liquefaction under the conditions at rather low temperatures between 300 and 400{degree}C, liquefaction products with high quality can be obtained by suppressing the aromatization of naphthene rings, but it was a problem that the reaction rate is slow. For improving this point, results obtained by changing solvents have been reported. In this study, to accelerate the liquefaction reaction, Illinois No.6 coal was liquefied in tetralin at temperature range from 300 to 400{degree}C by adding a given amount of sulfur or hydrogen sulfide at the initial stage of liquefaction. The addition of sulfur or hydrogen sulfide provided an acceleration effect of liquefaction reaction at temperature range between 300 and 400{degree}C. The addition of sulfur or hydrogen sulfide at 400{degree}C increased the oil products. At 370 and 400{degree}C, the liquid yield by adding sulfur was slightly higher than that by adding hydrogen sulfide, unexpectedly. The effects of sulfur and hydrogen sulfide were reversed when increasing the hydrogen pressure. 5 figs., 1 tab.

  11. Estimation of hydrogen bondings in coal utilizing FTir and differential scanning calorimetry (DSC); FTir to DSC wo mochiita sekitannai suiso ketsugo no teiryoteki hyoka no kokoromi

    Energy Technology Data Exchange (ETDEWEB)

    Mae, K.; Miura, K. [Kyoto University, Kyoto (Japan). Faculty of Engineering

    1996-10-28

    With an objective to know coal condensation structure which has influence on coal conversion reaction, an attempt was made on quantitative evaluation of hydrogen bonding in coal. Using as test samples the VDC made from Taiheiyo coal swollen by tetralin and vacuum-dried, and its pyrolyzed char, DSC measurement and Fourier transform infrared spectroscopy (FT) were performed. An FT spectrum comparison revealed that the VDC swollen at 220{degree}C has the hydrogen bonding relaxed partly from the original coal. However, since the change is in a huge coal molecular structure restraining space, it has stopped at relaxation of the bonding energy without causing separation as far as free radicals. On the other hand, the DSC curve shows that the VDC has slower endothermic velocity than the original coal. In other words, the difference in heat absorption amounts in both materials is equivalent to the difference of enthalpy ({Delta} H) of both materials, which corresponds to the relaxation of the hydrogen bonding. Therefore, the {Delta} H was related to wavenumber shift of the FT spectra (which corresponds to change in the hydrogen bonding condition). By using this relationship, a method for evaluating hydrogen bonding distribution was proposed from an O-H contracting vibration change that can be measured by using the FT spectra and a thermal change that can be measured by using the DSC. 3 refs., 7 figs.

  12. Chemical reaction between single hydrogen atom and graphene

    International Nuclear Information System (INIS)

    Ito, Atsushi; Nakamura, Hiroaki; Takayama, Arimichi

    2007-04-01

    We study chemical reaction between a single hydrogen atom and a graphene, which is the elemental reaction between hydrogen and graphitic carbon materials. In the present work, classical molecular dynamics simulation is used with modified Brenner's empirical bond order potential. The three reactions, that is, absorption reaction, reflection reaction and penetration reaction, are observed in our simulation. Reaction rates depend on the incident energy of the hydrogen atom and the graphene temperature. The dependence can be explained by the following mechanisms: (1) The hydrogen atom receives repulsive force by π-electrons in addition to nuclear repulsion. (2) Absorbing the hydrogen atom, the graphene transforms its structure to the 'overhand' configuration such as sp 3 state. (3) The hexagonal hole of the graphene is expanded during the penetration of the hydrogen atom. (author)

  13. Catalytic activation of molecular hydrogen in alkyne hydrogenation reactions by lanthanide metal vapor reaction products

    International Nuclear Information System (INIS)

    Evans, W.J.; Bloom, I.; Engerer, S.C.

    1983-01-01

    A rotary metal vapor was used in the synthesis of Lu, Er, Nd, Sm, Yb, and La alkyne, diene, and phosphine complexes. A typical catalytic hydrogenation experiment is described. The lanthanide metal vapor product is dissolved in tetrahydrofuran or toluene and placed in a pressure reaction vessel 3-hexyne (or another substrate) is added, the chamber attached to a high vacuum line, cooled to -196 0 C, evacuated, warmed to ambient temperature and hydrogen is added. The solution is stirred magnetically while the pressure in monitored. The reaction products were analyzed by gas chromatography. Rates and products of various systems are listed. This preliminary survey indicates that catalytic reaction chemistry is available to these metals in a wide range of coordination environments. Attempts to characterize these compounds are hampered by their paramagnetic nature and their tendency to polymerize

  14. Novel technique for coal pyrolysis and hydrogenation product analysis

    Energy Technology Data Exchange (ETDEWEB)

    Pfefferle, L.D.

    1992-01-01

    This report covers the last quarter of the last year of the three-year grant period. In the final project year, we concentrated on the pyrolysis and oxidative pyrolysis of large hydrocarbons and mixtures of large and small hydrocarbons in order to develop the VUV-MS technique for compounds more representative of those in coal pyrolysis applications. Special focus was directed at the pyrolysis and oxidative pyrolysis of benzene and benzene acetylene mixtures. The acetylene/benzene mixtures were used to gain a better understanding of the mechanisms of molecular growth in such systems specifically to look at the kinetics of aryl-aryl reactions as opposed to small molecule addition to phenyl radicals. Sarofim and coworkers at MIT have recently demonstrated the importance of these reactions in coal processing environments. In the past, the growth mechanism for the formation of midsized PAH has been postulated to involve primarily successive acetylene additions to phenyl-type radicals, our work confmns this as an important mechanism especially for smaller PAH but also investigates conditions where biaryl formation can play an important role in higher hydrocarbon formation.

  15. Analysis of the holistic impact of the Hydrogen Economy on the coal industry

    Science.gov (United States)

    Lusk, Shannon Perry

    As gas prices soar and energy demand continues to grow amidst increasingly stringent environmental regulations and an assortment of global pressures, implementing alternative energy sources while considering their linked economic, environmental and societal impacts becomes a more pressing matter. The Hydrogen Economy has been proposed as an answer to meeting the increasing energy demand for electric power generation and transportation in an environmentally benign way. Based on current hydrogen technology development, the most practical feedstock to fuel the Hydrogen Economy may prove to be coal via hydrogen production at FutureGen plants. The planned growth of the currently conceived Hydrogen Economy will cause dramatic impacts, some good and some bad, on the economy, the environment, and society, which are interlinked. The goal of this research is to provide tools to inform public policy makers in sorting out policy options related to coal and the Hydrogen Economy. This study examines the impact of a transition to a Hydrogen Economy on the coal industry by creating FutureGen penetration models, forecasting coal MFA's which clearly provide the impact on coal production and associated environmental impacts, and finally formulating a goal programming model that seeks the maximum benefit to society while analyzing the trade-offs between environmental, social, and economical concerns related to coal and the Hydrogen Economy.

  16. Reactions of butadiyne. 1: The reaction with hydrogen atoms

    Science.gov (United States)

    Schwanebeck, W.; Warnatz, J.

    1984-01-01

    The reaction of hydrogen (H) atoms with butadiene (C4H2) was studied at room temperature in a pressure range between w mbar and 10 mbar. The primary step was an addition of H to C4H2 which is in its high pressure range at p 1 mbar. Under these conditions the following addition of a second H atom lies in the transition region between low and high pressure range. Vibrationally excited C4H4 can be deactivated to form buten-(1)-yne-(3)(C4H4) or decomposes into two C2H2 molecules. The rate constant at room temperature for primary step is given. The second order rate constant for the consumption of buten-(1)-yne-(3) is an H atom excess at room temperature is given.

  17. Novel technique for coal pyrolysis and hydrogenation product analysis

    Energy Technology Data Exchange (ETDEWEB)

    Pfefferle, L.D.; Boyle, J.

    1993-03-15

    A microjet reactor coupled to a VUV photoionization time-of-flight mass spectrometer has been used to obtain species measurements during high temperature pyrolysis and oxidation of a wide range of hydrocarbon compounds ranging from allene and acetylene to cyclohexane, benzene and toluene. Initial work focused on calibration of the technique, optimization of ion collection and detection and characterization of limitations. Using the optimized technique with 118 nm photoionization, intermediate species profiles were obtained for analysis of the hydrocarbon pyrolysis and oxidation mechanisms. The soft'' ionization, yielding predominantly molecular ions, allowed the study of reaction pathways in these high temperature systems where both sampling and detection challenges are severe. Work has focused on the pyrolysis and oxidative pyrolysis of aliphatic and aromatic hydrocarbon mixtures representative of coal pyrolysis and hydropyrolysis products. The detailed mass spectra obtained during pyrolysis and oxidation of hydrocarbon mixtures is especially important because of the complex nature of the product mixture even at short residence times and low primary reactant conversions. The combustion community has advanced detailed modeling of pyrolysis and oxidation to the C4 hydrocarbon level but in general above that size uncertainties in rate constant and thermodynamic data do not allow us to a priori predict products from mixed hydrocarbon pyrolyses using a detailed chemistry model. For pyrolysis of mixtures of coal-derived liquid fractions with a large range of compound structures and molecular weights in the hundreds of amu the modeling challenge is severe. Lumped models are possible from stable product data.

  18. Coal pyrolysis under synthesis gas, hydrogen and nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Ariunaa, A.; Li Bao-Qing; Li Wen; Purevsuren, B. (and others) [Chinese Academy of Sciences, Taiyuan (China)

    2007-02-15

    Chinese Xundian, Mongolian Shiveeovoo lignites and Khoot oil shale are pyrolyzed under synthesis gas (SG) at temperature range from 400 to 800{sup o}C for lignite and from 300 to 600{sup o}C for oil shale with heating rate of 10{sup o}C/min in a fixed bed reactor. The results were compared with those obtained by pyrolysis under hydrogen and nitrogen. The results showed that unlike pyrolysis at high pressure, there are only slight different in the yields of char and tar among pyrolyses under various gases at room pressure for lignite, while higher liquid yield with lower yields of char and gas was obtained in pyrolysis of oil shale under SG and H{sub 2} than under N{sub 2}. It is found that the pyrite S can be easily removed to partially convert to organic S under various gaseous atmosphere and the total sulfur removal for oil shale is much less than lignite, which might be related to its high ash content. The higher total sulfur removal and less organic S content in the presence of SG in comparison with those under N{sub 2} and even under H{sub 2} in pyrolysis of Xundian lignite might result from the action of CO in SG. However, CO does not show its function in pyrolysis of Khoot oil shale, which might also be related to the high ash content. The results reported show the possibility of using synthesis gas instead of pure hydrogen as the reactive gas for coal hydropyrolysis. 11 refs., 4 figs., 6 tabs.

  19. 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

  20. COAL/POLYMER COPROCESSING WITH EFFICIENT USE OF HYDROGEN

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Linda J. Broadbelt; Matthew J. DeWitt; Hsi-Wu Wong

    2000-09-30

    The final project period was devoted to investigating the binary mixture pyrolysis of polypropylene and polystyrene. Their interactions were assessed in order to provide a baseline for experiments with multicomponent mixtures of polymers with coal. Pyrolysis of polypropylene, polystyrene and their binary mixture was investigated at temperatures of 350 C and 420 C with reaction times from 1 to 180 minutes. Two different loadings, 10 mg and 20 mg, were studied for neat polypropylene and polystyrene to assess the effect of total pressure on product yields and selectivities. For neat pyrolysis of polypropylene, total conversion was much higher at 420 C, and no significant effect of loading on the total conversion was observed. Four classes of products, alkanes, alkenes, dienes, and aromatic compounds, were observed, and their distribution was explained by a typical free radical mechanism. For neat polystyrene pyrolysis, conversion reached approximately 75% at 350 C, while at 420 C the conversion reached a maximum around 90% at 10 minutes and decreased at longer times because of condensation reactions. The selectivities to major products were slightly different for the two different loadings due to the effect of total reaction pressure on secondary reactions. For binary mixture pyrolysis, the overall conversion was higher than the average of the two neat cases. The conversion of polystyrene remained the same, but a significant enhancement in the polypropylene conversion was observed. This suggests that the less reactive polypropylene was initiated by polystyrene-derived radicals. These results are summarized in detail in an attached manuscript that is currently in preparation. The other results obtained during the lifetime of this grant are documented in the set of attached manuscripts.

  1. Achievement report for fiscal 1993 on research under Sunshine Program. Research on direct liquefaction reaction of coal; 1993 nendo sekitan no chokusetsu ekika hanno ni kansuru kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-03-01

    The reaction velocity constant of coal or the distribution of products in a high-pressure hydrocracking process of coal are found not to be affected by the temperature rise rate. The liquefaction of coal using CO and water is analyzed using a high-pressure differential thermal analyzer. The hydrogen gas generated during the water gas reaction reacts with CO for the formation of alcohols, carbonic acid, etc. The reaction rate is found to be higher when the specimen contains more oxygen. When coals greatly different from each other in terms of thermolytic reactivity, caking property, and intersolubility with medium oils are mixed, synergistic effects are exhibited, positive when active hydrogen supply is abundant and negative when it is short. In the case of the Hokkaido coal which contains 73.0-87.4% carbon, the grain diameter does not affect the liquefaction rate when the coal is crushed to the 48-mesh size approximately. Reaction velocity in direct liquefaction does not relate to hydrogen pressure. Asphaltenes in coal liquefaction are produced at the beginning of reaction, to be reduced in molecular weight due to cleavage of methylene crosslinks with the progress of reaction. Studies are conducted in a 0.1t/d-capable bench plant about liquefaction reaction characteristics and coal liquid properties, and chemical structures. (NEDO)

  2. Nuclear reaction analysis of hydrogen in materials: Principals and applications

    International Nuclear Information System (INIS)

    Lanford, W.A.

    1991-01-01

    Analysis for hydrogen in materials is difficult by most traditional analytic methods. Because hydrogen has no Auger transitions, no X-ray transitions, does not neutron activate, and does not backscatter ions, it is invisible in analytical methods based on these effects. In addition, since hydrogen is a universal contaminant in vacuum systems, techniques based on mass spectrometry are difficult unless extreme measures are taken to reduce hydrogen backgrounds. Because of this situation, methods have been developed for analyzing for hydrogen in solid materials based on nuclear reactions between bombarding ions and hydrogen atoms (protons) in the samples. The nuclear reaction methods are now practiced at laboratories around the world. The basic principals of nuclear reaction analysis will be briefly presented. This method will be illustrated by applications to problems ranging from basic physics, to geology, to materials science, and to art history and archeology

  3. Hydrogen production from coal gasification for effective downstream CO{sub 2} capture

    Energy Technology Data Exchange (ETDEWEB)

    Gnanapragasam, Nirmal V.; Reddy, Bale V.; Rosen, Marc A. [Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario, L1H 7K4 (Canada)

    2010-05-15

    The coal gasification process is used in commercial production of synthetic gas as a means toward clean use of coal. The conversion of solid coal into a gaseous phase creates opportunities to produce more energy forms than electricity (which is the case in coal combustion systems) and to separate CO{sub 2} in an effective manner for sequestration. The current work compares the energy and exergy efficiencies of an integrated coal-gasification combined-cycle power generation system with that of coal gasification-based hydrogen production system which uses water-gas shift and membrane reactors. Results suggest that the syngas-to-hydrogen (H{sub 2}) system offers 35% higher energy and 17% higher exergy efficiencies than the syngas-to-electricity (IGCC) system. The specific CO{sub 2} emission from the hydrogen system was 5% lower than IGCC system. The Brayton cycle in the IGCC system draws much nitrogen after combustion along with CO{sub 2}. Thus CO{sub 2} capture and compression become difficult due to the large volume of gases involved, unlike the hydrogen system which has 80% less nitrogen in its exhaust stream. The extra electrical power consumption for compressing the exhaust gases to store CO{sub 2} is above 70% for the IGCC system but is only 4.5% for the H{sub 2} system. Overall the syngas-to-hydrogen system appears advantageous to the IGCC system based on the current analysis. (author)

  4. Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

    Science.gov (United States)

    Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

    2016-12-01

    Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

  5. Desulfurization and denitrogenation in copyrolysis of coal with hydrogen-rich gases

    Energy Technology Data Exchange (ETDEWEB)

    Liao, H.; Li, B.; Zhang, B. [Chinese Academy of Sciences, Taiyuan (China). Institute of Coal Chemistry

    1999-06-01

    Desulfurization and denitrogenation were systematically investigated by analyzing the chars and tars from copyrolysis of Yanzhou high sulfur bituminous coal with coke-oven gas (COG), synthesis gas (SG) and hydrogen. The results indicated that under the conditions of 3MPa, up to 650{degree}C with a heating rate of 10{degree}C/min, the desulfurization of coal pyrolysis with COG, SG and hydrogen were almost equal (about 80%, w%, ad), the order of denitrogenation were: hydrogen (41%) {gt} SG(35%) {gt} COG(30%). The distributions of sulfur in char, oil and gas was very similar under the three reactive gases, i.e., about 205 in char, 105 in tar and 70% (diff.) in gas, respectively. Compared with hydropyrolysis at the same hydrogen partial pressure, the desulfurization of coal pyrolysis with coke oven gas was increased by about 4.5%, while the denitrogenation was decreased by about 3.5%. There is an important desulfurization advantage for hydropyrolysis using COG and SG instead of pure hydrogen. Compared with the copyrolysis of coal with COG, Yanzhou coal pyrolysis under SG can achieve the same level of desufurization but higher denitrogenation. 11 refs., 3 figs., 4 tabs.

  6. Optimization of hydrogen and syngas production from PKS gasification by using coal bottom ash.

    Science.gov (United States)

    Shahbaz, Muhammad; Yusup, Suzana; Inayat, Abrar; Patrick, David Onoja; Pratama, Angga; Ammar, Muhamamd

    2017-10-01

    Catalytic steam gasification of palm kernel shell is investigated to optimize operating parameters for hydrogen and syngas production using TGA-MS setup. RSM is used for experimental design and evaluating the effect of temperature, particle size, CaO/biomass ratio, and coal bottom ash wt% on hydrogen and syngas. Hydrogen production appears highly sensitive to all factors, especially temperature and coal bottom ash wt%. In case of syngas, the order of parametric influence is: CaO/biomass>coal bottom ash wt%>temperature>particle size. The significant catalytic effect of coal bottom ash is due to the presence of Fe 2 O 3 , MgO, Al 2 O 3 , and CaO. A temperature of 692°C, coal bottom ash wt% of 0.07, CaO/biomass of 1.42, and particle size of 0.75mm are the optimum conditions for augmented yield of hydrogen and syngas. The production of hydrogen and syngas is 1.5% higher in the pilot scale gasifier as compared to TGA-MS setup. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Simulation of pulverized coal fired boiler: reaction chamber

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, C.P.; Lansarin, M.A.; Secchi, A.R.; Mendes, T.F. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Dept. de Engenharia Quimica. Grupo de Modelagem, Simulacao, Controle e Otimizacao de Processos)]. E-mail: {cperdomo, marla, arge, talita}@enq.ufrgs.br

    2005-06-15

    This work is part of a joint project to built a computational tool for power plant simulation, dealing specifically with the reaction chamber (place of the boiler where the fuel is burned). In order to describe the conversion of chemical energy to thermal energy, an one dimensional pseudo-homogeneous mathematical model, with variable physical properties, and based on mass and energy balances, was developed. The equations were implemented in the gPROMS simulator and the model parameters were estimated using the module gEST of this software, with experimental data from a large-scale coal-fired utility boiler and kinetic data from the open literature. The results showed that the model predicts the composition of the outlet combustion gas satisfactorily. (author)

  8. A comparison of hydrogen with alternate energy forms from coal and nuclear energy

    International Nuclear Information System (INIS)

    Cox, K.E.

    1976-01-01

    Alternate energy forms that can be produced from coal and nuclear energy have been analyzed on efficiency, economic and end-use grounds. These forms include hydrogen, methane, electricity, and EVA-ADAM, a 'chemical heat pipe' approach to energy transmission. The EVA-ADAM system for nuclear heat appears to be economically competitive with the other energy carriers except over very large distances. The cost of hydrogen derived from coal is approximately equal to that of methane derived from the same source when compared on an equal BTU basis. Thermochemically derived hydrogen from nuclear energy shows a break-even range with hydrogen derived from coal at coal costs of from Pound33 to 80/ton depending on the cost of nuclear heat. Electricity and electrolytically derived hydrogen are the most expensive energy carriers and electricity's use should be limited to applications involving work rather than heat. Continued work in thermochemical hydrogen production schemes should be supported as an energy option for the future. (author)

  9. Theoretical studies of the reactions of HCN with atomic hydrogen

    International Nuclear Information System (INIS)

    Bair, R.A.; Dunning, T.H. Jr.

    1985-01-01

    A comprehensive theoretical study has been made of the energetics of the important pathways involved in the reaction of hydrogen atoms with hydrogen cyanide. For each reaction ab initio GVB-CI calculations were carried out to determine the structures and vibrational frequencies of the reactants, transition states, and products; then POL-CI calculations were carried out to more accurately estimate the electronic contribution to the energetics of the reactions. The hydrogen abstraction reaction is calculated to be endoergic by 24 kcal/mol [expt. ΔH (0 K) = 16--19 kcal/mol] with a barrier of 31 kcal/mol in the forward direction and 6 kcal/mol in the reverse direction. For the hydrogen addition reactions, addition to the carbon atom is calculated to be exoergic by 19 kcal/mol with a barrier of 11 kcal/mol, while addition to the nitrogen center is essentially thermoneutral with a barrier of 17 kcal/mol. Calculations were also carried out on the isomerization reactions of the addition products. The cis→trans isomerization of HCNH has a barrier of only 10 kcal/mol with the trans isomer being more stable by 5 kcal/mol. The (1,2)-hydrogen migration reaction, converting H 2 CN to trans-HCNH, is endoergic by only 14 kcal/mol, but the calculated barrier for the transfer is 52 kcal/mol. The energy of the migration pathway thus lies above that of the dissociation--recombination pathway

  10. Reaction of Aluminum with Water to Produce Hydrogen - 2010 Update

    Energy Technology Data Exchange (ETDEWEB)

    Petrovic, John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Thomas, George [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2011-06-01

    A Study of Issues Related to the Use of Aluminum for On-Board Vehicular Hydrogen Storage The purpose of this White Paper is to describe and evaluate the potential of aluminum-water reactions for the production of hydrogen for on-board hydrogen-powered vehicle applications. Although the concept of reacting aluminum metal with water to produce hydrogen is not new, there have been a number of recent claims that such aluminum-water reactions might be employed to power fuel cell devices for portable applications such as emergency generators and laptop computers, and might even be considered for possible use as the hydrogen source for fuel cell-powered vehicles.

  11. Hydrogen Fuel as Ecological Contribution to Operation of the Existing Coal-Fired Thermal Power Plants

    International Nuclear Information System (INIS)

    Cosic, D.

    2009-01-01

    The analysis is carried out of the application of a new hydrogen based alternative fuel as ecological contribution of the coal thermal power plants operation. Given the fact that coal thermal power plants are seen as the largest producers, not only of CO 2 , but of all others harmful gases, the idea is initiated to use the new alternative fuel as an additive to the coal which would result in much better performance of the coal power plants from an ecological point of view. It is possible to use such a fuel in relation of 10-30% of former coal use. The positive influence of such an application is much bigger than relative used quantity. This lecture has a goal to incite potential investors to create conditions for industrial testing of the new fuel. It will be very interesting to animate investors for large-scale production of the new fuel, too.(author).

  12. Achievement report for fiscal 1984 on Sunshine Program. Research on coal liquefaction reaction and the reforming and utilization of products; 1984 nendo sekitan no ekika hanno to seiseibutsu no kaishitsu riyo no kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1985-03-01

    Upon the development into a single law of the three liquefaction related laws, studies are started on coal liquefaction reaction and the reforming and utilization of the products. In the research on coal liquefaction reaction, the solvent ratio, change in reaction time, and change in liquefaction product constitution in case of repeated circulation of the solvent are tracked, and their relations with the liquefaction rate and yield are studied, these efforts involving the Taiheiyo coal, Yallourn coal, and the Miike coal. The Taiheiyo coal is subjected to a short-duration liquefaction reaction test. In the research on product reforming, the medium-gravity fraction from coal liquefaction is subjected to hydrogenation, and the effect of the reaction conditions on the properties and constitution of the thus-treated oil are studied. An SRC (solvent refined coal) solution of the Taiheiyo coal is subjected to hydrogenation in the presence of a Ni-Mo catalyst, and the SRC cracking rate and product properties are compared with those obtained from another solution treated with a Co-Mo catalyst. In the research on product utilization, the medium-gravity fraction from coal liquefaction is subjected to hydrogenation under three sets of different reaction conditions in the presence of a Ni-Mo/Al{sub 2}O{sub 3} based catalyst. In this process, specimens are prepared by mixing the original oil, its hydrogenated product, and a petroleum-based light oil, and a study is made about the usability of the specimens and their mixtures with petroleum-based heater oil as light oil or heater oil. (NEDO)

  13. Reaction between Hydrogen Sulfide and Limestone Calcines

    Czech Academy of Sciences Publication Activity Database

    Hartman, Miloslav; Svoboda, Karel; Trnka, Otakar; Čermák, Jiří

    2002-01-01

    Roč. 41, č. 10 (2002), s. 2392-2398 ISSN 0888-5885 R&D Projects: GA AV ČR IAA4072711; GA AV ČR IAA4072801 Keywords : hydrogen sulfide * limestone calcines * desulfurization Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.247, year: 2002

  14. Isotope exchange reactions in hydrogen mixtures

    International Nuclear Information System (INIS)

    Czaplinski, W.; Gula, A.; Kravtsov, A.; Mikhailov, A.; Popov, N.

    1990-12-01

    The rates of isotopic exchange for the excited states of muonic hydrogen are calculated as functions of collision energy. Ground state population q 1s for different collision energies, target densities and isotope concentrations is obtained. It is shown that for principal quantum numbers n > 5 the isotopic exchange still considerably influences the value of q 1s . (author)

  15. Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

    Science.gov (United States)

    Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

    2015-01-01

    Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

  16. Diels-Alder reactions onto fluorinated and hydrogenated graphene

    Science.gov (United States)

    Denis, Pablo A.

    2017-09-01

    We studied Diels-Alder (DA) reactions onto functionalized graphene. When fluorine, hydrogen or oxygen functional groups are present on one side of the sheet, the DA cycloadditions become significantly more exergonic when performed on the opposite side. Hydrogen is more effective than fluorine and oxygen to promote these cycloadditions. In contrast with the results obtained for perfect graphene, the functionalization with H, F or O turns the DA reactions exergonic, with ΔG°298 = -127.2 kcal/mol. The reaction barriers are expected to be considerably lowered with respect to perfect graphene because the functional groups significantly reduce the distortion energy.

  17. Overview of Light Hydrogen-Based Low Energy Nuclear Reactions

    Science.gov (United States)

    Miley, George H.; Shrestha, Prajakti J.

    This paper reviews light water and hydrogen-based low-energy nuclear reactions (LENRs) including the different methodologies used to study these reactions and the results obtained. Reports of excess heat production, transmutation reactions, and nuclear radiation emission are cited. An aim of this review is to present a summary of the present status of light water LENR research and provide some insight into where this research is heading.

  18. Reaction of O+, CO+, and CH+ ions with atomic hydrogen

    International Nuclear Information System (INIS)

    Federer, W.; Villinger, H.; Howorka, F.; Lindinger, W.; Tosis, P.; Bassi, D.; Ferguson, E.

    1984-01-01

    Rate coefficients for reactions of the ions O + , CO + , and CH + with atomic hydrogen have been measured for the first time at 300 K. This provides basic data for the ion chemistry of planetary atmospheres, cometary atmospheres, and interstellar molecular clouds. The O + +H measurement supports quantal calculations of this reaction. The CO + +H reaction provides an example of partial spin nonconservation in a charge-transfer reaction occurring in a deep potential well. Reactions of the same ions with H 2 that have been measured elsewhere are also reported

  19. Exchange reaction between tritiated hydrogen and water vapor

    International Nuclear Information System (INIS)

    Yamada, Koichi; Takano, Kenichi; Watanabe, Tamaki.

    1979-01-01

    Exchange reaction of tritiated hydrogen to water vapor under the condition of tritium gas concentration between 1 μCi/l and 1 mCi/l was studied. Tritium gas with hydrogen gas of 5 Torr and water of 20 mg were enclosed in a Pyrex glass ampule with volume of about 100 ml. The mixed gas with water vapor was heated with electric furnace. The heating time was between 2 and 100 hr, and the temperature was 776, 725, 675, 621, and 570.5 0 K. After heating, tritiated water was trapped with liquid nitrogen, and counted with a liquid scintillation counter. The radioactive concentration of initial tritiated hydrogen was measured with a calibrated ionization chamber. The main results obtained are as follows; 1) the concentration of produced tritiated water is well proportioned to that of initial tritiated hydrogen, 2) the activation energy of exchange reaction from tritiated hydrogen to tritiated water is 26.2 kcal/mol and that of inverse reaction is 27.4 kcal/mol, 3) the reaction rate at room temperature which calculated with activation energy is 1.04 x 10 -13 day -1 , and then exchange reaction at room temperature is negligible. (author)

  20. Coal chemistry. 8. Reactions of tetralin with coal and with some carbon-14-containing model compounds

    International Nuclear Information System (INIS)

    Collins, C.J.; Raaen, V.F.; Benjamin, B.M.; Maupin, P.H.; Roark, W.H.

    1979-01-01

    When coal was treated with tetralin-l- 14 C at 400 0 C, small yields of α- and β-methylnaphthalenes- 14 C were observed. In order to determine the mechanism of the reaction, tetralin was heated with 14 C-labeled 1,3-diphenylpropanes (1), with 1,3-diphenylpropene (2), and with 14 C-labeled phenetoles (3). In each case methylnaphthalenes were observed, and the origins of the methyl groups were determined with carbon-14. In addition to the methylnaphthalenes, 1 and 2 also yielded toluene and ethylbenzene (after 19 h), whereas phenetole-β- 14 C (3-β- 14 C) yielded toluene (unlabeled) plus ethyl- 14 C-benzene, benzene, phenol, and a mixture of α- and β-ethyl- 14 C-naphthalenes. Crossover experiments with labeled phenetole and unlabeled ethyl p-tolyl ether proved the intramolecularity of the reaction phenetole → toluene + ethylbenzene, thus illustrating a 1,2-phenyl shift from oxygen to carbon

  1. Hydrogen addition reactions of aliphatic hydrocarbons in comets

    Science.gov (United States)

    Kobayashi, Hitomi; Watanabe, N.; Watanabe, Y.; Fukushima, T.; Kawakita, H.

    2013-10-01

    Comets are thought as remnants of early solar nebula. Their chemical compositions are precious clue to chemical and physical evolution of the proto-planetary disk. Some hydrocarbons such as C2H6, C2H2 and CH4 in comets have been observed by using near-infrared spectroscopy. Although the compositions of C2H6 were about 1% relative to the water in normal comets, there are few reports on the detection of C2H6 in ISM. Some formation mechanisms of C2H6 in ISM have been proposed, and there are two leading hypotheses; one is the dimerizations of CH3 and another is the hydrogen addition reactions of C2H2 on cold icy grains. To evaluate these formation mechanisms for cometary C2H6 quantitatively, it is important to search the C2H4 in comets, which is the intermediate product of the hydrogen addition reactions toward C2H6. However, it is very difficult to detect the C2H4 in comets in NIR (3 microns) regions because of observing circumstances. The hydrogen addition reactions of C2H2 at low temperature conditions are not well characterized both theoretically and experimentally. For example, there are no reports on the reaction rate coefficients of those reaction system. To determine the production rates of those hydrogen addition reactions, we performed the laboratory experiments of the hydrogenation of C2H2 and C2H4. We used four types of the initial composition of the ices: pure C2H4, pure C2H2, C2H2 on amorphous solid water (ASW) and C2H4 on ASW at three different temperatures of 10, 20, and 30K. We found 1) reactions are more efficient when there are ASW in the initial compositions of the ice; 2) hydrogenation of C2H4 occur more rapid than that of C2H2.

  2. Numerical Simulation of Hydrogen Combustion: Global Reaction Model and Validation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yun [School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an (China); Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY (United States); Liu, Yinhe, E-mail: yinheliu@mail.xjtu.edu.cn [School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an (China)

    2017-11-20

    Due to the complexity of modeling the combustion process in nuclear power plants, the global mechanisms are preferred for numerical simulation. To quickly perform the highly resolved simulations with limited processing resources of large-scale hydrogen combustion, a method based on thermal theory was developed to obtain kinetic parameters of global reaction mechanism of hydrogen–air combustion in a wide range. The calculated kinetic parameters at lower hydrogen concentration (C{sub hydrogen} < 20%) were validated against the results obtained from experimental measurements in a container and combustion test facility. In addition, the numerical data by the global mechanism (C{sub hydrogen} > 20%) were compared with the results by detailed mechanism. Good agreement between the model prediction and the experimental data was achieved, and the comparison between simulation results by the detailed mechanism and the global reaction mechanism show that the present calculated global mechanism has excellent predictable capabilities for a wide range of hydrogen–air mixtures.

  3. Numerical Simulation of Hydrogen Combustion: Global Reaction Model and Validation

    International Nuclear Information System (INIS)

    Zhang, Yun; Liu, Yinhe

    2017-01-01

    Due to the complexity of modeling the combustion process in nuclear power plants, the global mechanisms are preferred for numerical simulation. To quickly perform the highly resolved simulations with limited processing resources of large-scale hydrogen combustion, a method based on thermal theory was developed to obtain kinetic parameters of global reaction mechanism of hydrogen–air combustion in a wide range. The calculated kinetic parameters at lower hydrogen concentration (C hydrogen < 20%) were validated against the results obtained from experimental measurements in a container and combustion test facility. In addition, the numerical data by the global mechanism (C hydrogen > 20%) were compared with the results by detailed mechanism. Good agreement between the model prediction and the experimental data was achieved, and the comparison between simulation results by the detailed mechanism and the global reaction mechanism show that the present calculated global mechanism has excellent predictable capabilities for a wide range of hydrogen–air mixtures.

  4. Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

    Science.gov (United States)

    Li, Yuanchao; Nguyen, Trung Van

    2018-04-01

    Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.

  5. Hydrogen production by co-gasification of coal and renewables

    Energy Technology Data Exchange (ETDEWEB)

    Fermoso, J.; Arias, B.; Rubiera, F.; Arenillas, A.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo, (Spain)

    2006-07-01

    In this work, co-gasification of two coals with samples of pet-coke, sewage sludge and biomass was conducted at atmospheric pressure in a fixed bed reactor under steam/oxygen atmosphere, in order to evaluate possible synergistic effects during co-gasification. Experiments carried out at non-isothermal conditions for blends of a low volatile bituminous coal and dried sewage sludge, indicated the absence of interactive effects between the blends. The concentration of H{sub 2} and CO could be predicted from the concentrations of the individual components in the blends and their respective mass fractions. The results obtained under isothermal (1000 C) conditions for blends of a high ash coal with pet-coke, and blends with biomass (chestnut) produced less gas yield than the theoretically calculated. However, for the mixtures of coal and biomass the quality of the syngas, expressed by the amount of the produced H{sub 2}+CO and by the H{sub 2}/CO ratio, was not altered. (authors)

  6. Hydrogen production by co-gasification of coal and renewables

    International Nuclear Information System (INIS)

    Fermoso, J.; Arias, B.; Rubiera, F.; Arenillas, A.; Pis, J.J.

    2006-01-01

    In this work, co-gasification of two coals with samples of pet-coke, sewage sludge and biomass was conducted at atmospheric pressure in a fixed bed reactor under steam/oxygen atmosphere, in order to evaluate possible synergistic effects during co-gasification. Experiments carried out at non-isothermal conditions for blends of a low volatile bituminous coal and dried sewage sludge, indicated the absence of interactive effects between the blends. The concentration of H 2 and CO could be predicted from the concentrations of the individual components in the blends and their respective mass fractions. The results obtained under isothermal (1000 C) conditions for blends of a high ash coal with pet-coke, and blends with biomass (chestnut) produced less gas yield than the theoretically calculated. However, for the mixtures of coal and biomass the quality of the syngas, expressed by the amount of the produced H 2 +CO and by the H 2 /CO ratio, was not altered. (authors)

  7. Production of hydrogen by direct gasification of coal with steam using nuclear heat

    Science.gov (United States)

    1975-01-01

    Problems related to: (1) high helium outlet temperature of the reactor, and (2) gas generator design used in hydrogen production are studied. Special attention was given to the use of Oklahoma coal in the gasification process. Plant performance, operation, and environmental considerations are covered.

  8. The reactions of oxygen and hydrogen with liquid sodium

    International Nuclear Information System (INIS)

    Ullmann, H.

    1981-01-01

    Results so far available as to the reactions and chemical equilibrium of oxygen and hydrogen with liquid sodium have been analyzed critically. The enthalpy values of the reactions have been discussed and supplemented on the basis of corresponding BORN-HABER cycles. The concentration and temperature functions of the hydrogen equilibrium pressure were deduced from experimental results. In relation to the solubility data the solid phases coexisting with liquid sodium in the ternary system Na-O-H have been discussed. The reaction of oxygen with hydrogen in diluted solution in liquid sodium has been investigated in more detail. Interaction coefficients, and the temperature functions of the free energy of formation and the equilibrium constant have been determined. (orig.)

  9. Destruction of oxalate by reaction with hydrogen peroxide. [Hydrazine oxalate

    Energy Technology Data Exchange (ETDEWEB)

    Mailen, J.C.; Tallent, O.K.; Arwood, P.C.

    1981-09-01

    The destruction of oxalate by oxidation to carbon dioxide using hydrogen peroxide was studied as an alternative method for the disposal of oxalate in connection with the possible use of an aqueous hydrazine oxalate solution as a scrubbing agent for solvent cleanup in processes for the recovery of uranium, plutonium, and thorium by solvent extraction. The rate of oxidation of oxalate by hydrogen peroxide in acid solution at the reflux temperature was adequate for process application; reaction half-times at 100/sup 0/C were less than one hour when the hydrogen peroxide concentration was greater than 0.5 M. The reaction was first order with respect to both the oxalate and hydrogen peroxide concentrations and had an activation energy of 58.7 kJ/g-mol. The rate increased with the hydrogen ion concentration as (H/sup +/)/sup 0/ /sup 3/ but was not significantly affected by the presence of 100 ppM of uranium or copper in solution. In the near-neutral hydrazine oxalate solutions, the reaction of either component with hydrogen peroxide was too slow for process application.

  10. A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Maria Michela Dell’Anna

    2010-05-01

    Full Text Available Catalytic hydrogenation under mild conditions of olefins, unsaturated aldeydes and ketones, nitriles and nitroarenes was investigated, using a supported rhodium complex obtained by copolymerization of Rh(cod(aaema [cod: 1,5-cyclooctadiene, aaema–: deprotonated form of 2-(acetoacetoxyethyl methacrylate] with acrylamides. In particular, the hydrogenation reaction of halonitroarenes was carried out under 20 bar hydrogen pressure with ethanol as solvent at room temperature, in order to minimize hydro-dehalogenation. The yields in haloanilines ranged from 85% (bromoaniline to 98% (chloroaniline.

  11. Hydrogen release from irradiated elastomers measured by Nuclear Reaction Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Jagielski, J., E-mail: jacek.jagielski@itme.edu.pl [Institute for Electronic Materials Technology, Wolczynska 133, 01-926 Warszawa (Poland); National Centre for Nuclear Research, A. Soltana 7, 05-400 Swierk/Otwock (Poland); Ostaszewska, U. [Institute for Engineering of Polymer Materials & Dyes, Division of Elastomers & Rubber Technology, Harcerska 30, 05-820 Piastow (Poland); Bielinski, D.M. [Technical University of Lodz, Institute of Polymer & Dye Technology, Stefanowskiego 12/16, 90-924 Lodz (Poland); Grambole, D. [Institute of Ion Beam Physics and Materials Research, Helmholtz Zentrum Dresden Rossendorf, PO Box 51 01 19, D-01314 Dresden (Germany); Romaniec, M.; Jozwik, I.; Kozinski, R. [Institute for Electronic Materials Technology, Wolczynska 133, 01-926 Warszawa (Poland); Kosinska, A. [National Centre for Nuclear Research, A. Soltana 7, 05-400 Swierk/Otwock (Poland)

    2016-03-15

    Ion irradiation appears as an interesting method of modification of elastomers, especially friction and wear properties. Main structural effect caused by heavy ions is a massive loss of hydrogen from the surface layer leading to its smoothening and shrinking. The paper presents the results of hydrogen release from various elastomers upon irradiation with H{sup +}, He{sup +} and Ar{sup +} studied by using Nuclear Reaction Analysis (NRA) method. The analysis of the experimental data indicates that the hydrogen release is controlled by inelastic collisions between ions and target electrons. The last part of the study was focused on preliminary analysis of mechanical properties of irradiated rubbers.

  12. Reactions on carbonaceous materials with hydrogenating gases

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M; Simon, W; Kronig, W

    1933-02-08

    A process is given for the production of valuable hydrocarbons by treatment of distillable carbonaceous materials with added hydrogenating gases under pressure in contact with catalysts. The process comprises adding to the initial materials before or during the said treatment organic sulphonic acids together with metals of groups 4 to 8 of the periodic system or compounds thereof, or free organic carboxylic acids which when inorganic salts are simultaneously present do not combine therewith to form complex ansolvo acids, or acid salts of strong acids or acid salts of heavy metals, lithium, magnesium, and aluminum, with the exception of aluminum hydrosilicates, or inorganic oxygen containing acids of sulfur or nitrogen or the anhydrides of said inorganic oxygen-containing acids.

  13. Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

    International Nuclear Information System (INIS)

    Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

    1993-01-01

    Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

  14. Hydrogen transfer reactions of interstellar Complex Organic Molecules

    Science.gov (United States)

    Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

    2018-06-01

    Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

  15. Reaction between vanadium trichloride oxide and hydrogen sulfide

    International Nuclear Information System (INIS)

    Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

    1978-01-01

    The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

  16. Novel Magnetically Fluidized Bed Reactor Development for the Looping Process: Coal to Hydrogen Production R&D

    Energy Technology Data Exchange (ETDEWEB)

    Mei, Renwei; Hahn, David; Klausner, James; Petrasch, Jorg; Mehdizadeh, Ayyoub; Allen, Kyle; Rahmatian, Nima; Stehle, Richard; Bobek, Mike; Al-Raqom, Fotouh; Greek, Ben; Li, Like; Chen, Chen; Singh, Abhishek; Takagi, Midori; Barde, Amey; Nili, Saman

    2013-09-30

    The coal to hydrogen project utilizes the iron/iron oxide looping process to produce high purity hydrogen. The input energy for the process is provided by syngas coming from gasification process of coal. The reaction pathways for this process have been studied and favorable conditions for energy efficient operation have been identified. The Magnetically Stabilized Porous Structure (MSPS) is invented. It is fabricated from iron and silica particles and its repeatable high performance has been demonstrated through many experiments under various conditions in thermogravimetric analyzer, a lab-scale reactor, and a large scale reactor. The chemical reaction kinetics for both oxidation and reduction steps has been investigated thoroughly inside MSPS as well as on the surface of very smooth iron rod. Hydrogen, CO, and syngas have been tested individually as the reducing agent in reduction step and their performance is compared. Syngas is found to be the most pragmatic reducing agent for the two-step water splitting process. The transport properties of MSPS including porosity, permeability, and effective thermal conductivity are determined based on high resolution 3D CT x-ray images obtained at Argonne National Laboratory and pore-level simulations using a lattice Boltzmann Equation (LBE)-based mesoscopic model developed during this investigation. The results of those measurements and simulations provide necessary inputs to the development of a reliable volume-averaging-based continuum model that is used to simulate the dynamics of the redox process in MSPS. Extensive efforts have been devoted to simulate the redox process in MSPS by developing a continuum model consist of various modules for conductive and radiative heat transfer, fluid flow, species transport, and reaction kinetics. Both the Lagrangian and Eulerian approaches for species transport of chemically reacting flow in porous media have been investigated and verified numerically. Both approaches lead to correct

  17. Experimental study on steam gasification of coal using molten blast furnace slag as heat carrier for producing hydrogen-enriched syngas

    International Nuclear Information System (INIS)

    Duan, Wenjun; Yu, Qingbo; Wu, Tianwei; Yang, Fan; Qin, Qin

    2016-01-01

    Highlights: • New method for producing HRG by gasification using BFS as heat carrier was proposed. • The continuous experiment of steam gasification in molten BFS was conducted. • The hydrogen-enriched syngas was produced by this method. • The molten BFS waste heat was utilized effectively by steam gasification. • This method could be widely used in steam gasification of different types of coal. - Abstract: The new method for producing hydrogen-enriched syngas (HRG) by steam gasification of coal using molten blast furnace slag (BFS) as heat carrier was established. In order to achieve the HRG production, a gasification system using this method was proposed and constructed. The carbon gasification efficiency (CE), hydrogen yield (YH_2) and cold gasification efficiency (CGE) in the molten slag reactor were measured, and the effects of temperature, S/C (steam to coal) ratio and coal type on the reaction performance were accessed. The results indicated that the preferred temperature was 1350 °C, which ensured the miscibility of coal–steam–slag, the diffusion of reactant in molten BFS as well as recovering waste heat. The optimal S/C ratio was 1.5–2.0 for producing HRG. Under these conditions, the hydrogen fraction was higher than 63% and the gas yield reached to 1.89 Nm"3/kg. The CE and CGE were higher than 96% and 102%, respectively. The YH_2 also reached to 1.20 Nm"3/kg. Meanwhile, different types of coal were successfully gasified in molten BFS reactor for producing HRG. The proposed method enhanced the gasification efficiency of different types of coal, recovered the BFS waste heat effectively, and had important guidance for industrial manufacture.

  18. Report on the achievements in the Sunshine Project in fiscal 1986. Studies on coal liquefying reactions, and product reforming and utilization; 1981 nendo sekitan no ekika hanno to seiseibutsu no kaishitsu riyo no kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1982-03-01

    The study items for the current fiscal year are as follows: (1) fundamental studies on coal liquefying reactions, (2) studies on product reforming, and (3) studies on product utilization. In Item 1, investigations were given on effects of hydrogenation treatment for a heavy circulation solvent in the coal liquefying reactions imposed on yield and nature of the product oil. Liquefying reactions were carried out under the presence of various heavy solvents having different hydrogen donating performances, or iron-based and oil soluble solvents. Liquefaction rates, yields and natures of different products were analyzed to discuss the degree of hydrogen donating performance of the solvents, the using conditions for the catalysts in the primary liquefying reaction, and the reaction conditions to enhance the product oil yield. In Item 2, hydrogenation treatment was given on the heavy oil fraction of the product oil obtained from the liquefying reaction using a heavy circulating solvent. The result was compared with the result on the medium oil fraction. Light oil fraction obtained from brown coal liquefaction was reformed to manufacture the reformed oil for engine tests. In Item 3, nature analysis and combustion tests were performed on the light oil fraction of the liquefied oil using brown coal as the material, and on the hydrogenated oil as a diesel engine fuel. The reforming effects were discussed from the amount and nature of the exhaust gas. (NEDO)

  19. Measurement of hydrogen in BCN films by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Yasui, Haruyuki; Hirose, Yukio; Sasaki, Toshihiko [Kanazawa Univ. (Japan); Awazu, Kaoru [Industrial Research Inst., of Ishikawa, Kanazawa (Japan); Naramoto, Hiroshi [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

    2001-07-01

    Hydrogen is a very common contaminant in carbon films. It can strongly influence on mechanical, physical and chemical properties of the films. The analysis of hydrogen is therefore a crucial problem produce the films with the properties required. Ion beam techniques using nuclear reactions are effective for the quantitative determination of hydrogen concentration. A specially designed spectrometer is employed for the detailed determination of hydrogen concentrations by detecting 4.43MeV {gamma}-rays from the resonant nuclear reactions {sup 1}H({sup 15}N, {alpha}{gamma}){sup 12}C at the 6.385MeV. In this study, the BCN films were formed on silicon substrate by ion beam assisted deposition (IBAD), in which boron and carbon were deposited by electron beam heating of B{sub 4}C solid and nitrogen was supplied by ion implantation simultaneously. The concentrations of hydrogen in BCN films were measured using RNRA. The mechanical properties of BCN films were evaluated using an ultra-micro-hardness tester. It was confirmed that the hardness of BCN films increased with increasing the concentration of hydrogen. (author)

  20. Influence of catalytic activity and reaction conditions on the product distribution in coal liquefaction; Sekitan ekikayu no seiseibutsu bunpu ni taisuru shokubai kassei oyobi hanno joken no eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Hasuo, H.; Sakanishi, K.; Mochida, I. [Kyushu University, Fukuoka (Japan). Institute of Advanced Material Study

    1996-10-28

    The NiMo sulfide supported on Ketjen Black (KB) was more effective and yielded lighter oil products containing light fractions with their boiling point below 300{degree}C during the two stage liquefaction combining low temperature and high temperature hydrogenation the conventional NiMo/alumina catalyst and FeS2 catalyst. Although the NiMo/alumina yielded increased oil products during the two stage liquefaction, the lighter oil fractions did not increase and the heavier fractions increased mainly. This suggests that the hydrogenation of aromatic rings and successive cleavage of the rings are necessary for producing the light oil, which is derived from the sufficient hydrogenation of aromatic rings using catalysts. For the two stage reaction with NiMo/KB catalyst, it was considered that sufficient hydrogen was directly transferred to coal molecules at the first stage of the low temperature reaction, which promoted the solubilization of coal and the successive hydrogenation at the high temperature reaction. Thus, high activity of the catalyst must be obtained. It is expected that further high quality distillates can be produced through the optimization of catalysts and solvents at the two stage reaction. 1 ref., 4 figs., 1 tab.

  1. Report on the achievements in the Sunshine Project in fiscal 1985. Studies on liquefying reaction of coals, and on reforming and utilizing the product; 1985 nendo sekitan no ekika hanno to seiseibutsu no kaishitsu riyo no kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1986-03-01

    Contents of the studies on coal liquefaction processes during fiscal 1985 are as follows: coal liquefying reaction using iron based catalysts and adding solvent-refined coal (SRC) into the solvent is carried out by using an autoclave to investigate changes in the liquefaction rate, solvent and SRC; coal hydrogenating reaction using iron based catalysts is performed by using a continuous liquefying equipment to discuss sedimentation and accumulation of the catalysts, coal types, and conversion rate; hydrogenation treatment using Ni-Mo based catalysts is given on residual products produced by the liquefaction to compare degree of lightening and cleanliness with the result in medium fraction; hydrogenation treatment is given on the medium fraction produced in a large process to investigate effects of the reforming treatment from the nature of the produced oil and compare the effects with the nature of oil produced from mixing the medium fraction of the coal liquefied oil with the corresponding fraction from petroleum; a combustion test using a diesel engine is performed on oil reformed and produced from the hydrogenation treatment of the medium fraction of the coal liquefied oil to discuss the reforming effect from the amount and nature of the waste gas; and the oil mixed of the medium fraction and the corresponding fraction in petroleum is evaluated on petroleum substitution performance by using the above test. (NEDO)

  2. Greenhouse gas implications of using coal for transportation: Life cycle assessment of coal-to-liquids, plug-in hybrids, and hydrogen pathways

    International Nuclear Information System (INIS)

    Jaramillo, Paulina; Samaras, Constantine; Wakeley, Heather; Meisterling, Kyle

    2009-01-01

    Using coal to produce transportation fuels could improve the energy security of the United States by replacing some of the demand for imported petroleum. Because of concerns regarding climate change and the high greenhouse gas (GHG) emissions associated with conventional coal use, policies to encourage pathways that utilize coal for transportation should seek to reduce GHGs compared to petroleum fuels. This paper compares the GHG emissions of coal-to-liquid (CTL) fuels to the emissions of plug-in hybrid electric vehicles (PHEV) powered with coal-based electricity, and to the emissions of a fuel cell vehicle (FCV) that uses coal-based hydrogen. A life cycle approach is used to account for fuel cycle and use-phase emissions, as well as vehicle cycle and battery manufacturing emissions. This analysis allows policymakers to better identify benefits or disadvantages of an energy future that includes coal as a transportation fuel. We find that PHEVs could reduce vehicle life cycle GHG emissions by up to about one-half when coal with carbon capture and sequestration is used to generate the electricity used by the vehicles. On the other hand, CTL fuels and coal-based hydrogen would likely lead to significantly increased emissions compared to PHEVs and conventional vehicles using petroleum-based fuels.

  3. Hydrogen/Chlorine exchange reactions of gaseous carbanions.

    Science.gov (United States)

    Chen, Hao; Cooks, R Graham; Meurer, Eduardo C; Eberlin, Marcos N

    2005-12-01

    Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.

  4. Filtration and Hydrogen Reaction Modeling in a Depleted Uranium Bed

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Kwang Jin; Kim, Yean Jin; Ahn, Do Hee; Chung, Hong Suk [UST, Daejeon (Korea, Republic of); Kang, Hee Seok [KAERI, Daejeon (Korea, Republic of); Yun, Sei Hun [NFRI, Daejeon (Korea, Republic of)

    2016-05-15

    The storage and delivery system (SDS) stores the hydrogen isotopes and delivers them to the fuel injection system. Depleted uranium (DU) was chosen as a hydrogen isotope storage material. The hydrogen isotopes stored in the SDS are in the form of DU hydride confined in the primary and secondary containment within a glove box with an argon atmosphere. In this study, we performed a modeling study of the SDS. A modeling study is practically important because an experimental study requires comparatively more money and time. We estimated the hydrogen atomic ratio in DU hydride by two empirical equations we formulated. Two empirical equations are used to determine Pressure-Composition-Temperature (PCT) curves and the hydrogen atomic ratio in DU hydride. In addition, we present the effect of pressure and temperature in the hydriding and dehydriding. A modeling study of the SDS was performed in this study. It is practically important to save more money and time. The hydrogen atomic ratio in the DU hydride was estimated using two empirical equations. The two empirical equations are modified and reformulated to determine PCT curves and the hydrogen atomic ratio in DU hydride. All parameters that are required to solve two empirical equations are obtained from the experimental data. The derived parameters are utilized for the numerical simulations. In the numerical simulations, the effects of pressure and temperature on both the hydriding and dehydriding reaction rates are confirmed.

  5. Investigation on hydrogen permeation on heat exchanger materials in conditions of steam coal gasification

    International Nuclear Information System (INIS)

    Moellenhoff, H.

    1984-01-01

    The permeation of hydrogen through iron-based alloys of different compositions in the temperature range between 700 and 1000 0 C was examined in a laboratory fluidized bed in the conditions of steam/coal gasification. Apart from tests on bright metal samples, measurement in the gasification atmosphere at a maximum pressure of 1 bar were carried out during oxidation of the metal. Experiments in a steam/hydrogen/argon mixture with the same oxidation potential were used for comparison purposes. The hydrogen permeated through the metal sample was taken to a gas chromatograph with argon flushing gas and analyzed there. The investigations on bright steel samples of various composition showed that their permeabilities for hydrogen at temperatures around 900 0 C only differed by a maximum of ± 30%. Effective prevention of permeation is therefore not possible simply by choosing a suitable alloy. If the steels are oxidized during permeation measurements, there is a reduction of the hydrogen permeability by 2 or 3 orders of magnitude due to the oxidation process, both in the steam/coal gasification fluidized bed and in a pure steam/hydrogen/argon mixture. (orig./GG) [de

  6. Hydrogen isotope exchange reaction rates in tritium, hydrogen and deuterium mixed gases

    International Nuclear Information System (INIS)

    Uda, Tatsuhiko

    1992-01-01

    Hydrogen isotope exchange reaction rates in H 2 +T 2 , D 2 +T 2 and H 2 +D 2 +T 2 mixed gases, as induced by tritium decay and beta radiation, were experimentally measured by laser Raman spectrometry. Initially a glass cell was filled with T 2 gas to a pressure of 30-40 kPa, and an equivalent partial pressure of H 2 and/or D 2 was added. The first-order hydrogen isotope exchange reaction rates were 5.54x10 -2 h -1 for H 2 +T 2 mixed gas and 4.76x10 -2 h -1 for D 2 +T 2 . The actual HT producing rate was nearly equivalent to the rate of DT, but the reverse reaction rate of HT was faster than that of DT. The exchange reaction rates between H, D and T showed the isotope effect, HD>HT>DT. The hydrogen isotope exchange reaction rates observed were about twenty times larger than ion formation rates by beta radiation. This result suggests that a free radical chain reaction in hydrogen isotopes is occurring. (orig.)

  7. 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.

  8. The electrochemical Peltier heat of the standard hydrogen electrode reaction

    International Nuclear Information System (INIS)

    Fang Zheng; Wang Shaofen; Zhang Zhenghua; Qiu Guanzhou

    2008-01-01

    A method for measuring the electrochemical Peltier heat (EPH) of a single electrode reaction has been developed and an absolute scale is suggested to obtain EPH of the standard hydrogen electrode. The scale is based on φ 0 * = 0 and ΔS 0 * = 0 for any electrode reaction at zero Kelvin, in accord with the third law of thermodynamics. The relationships between entropy, enthalpy and free energy changes on this scale and on the conventional scale are derived. Calorimetric experiments were made on the Fe(CN) 6 3- /Fe(CN) 6 4- system at five different concentrations at 298.15 K, and EPH for the standard hydrogen electrode reaction is obtained. EPHs and the entropy change on the absolute scale for the studied redox are linearly related to concentration of electrolyte. The reversible electric work is almost concentration independent in the range of concentration studied

  9. FUNDAMENTAL KINETICS OF SUPERCRITICAL COAL LIQUEFACTION: EFFECT OF CATALYSTS AND HYDROGEN-DONOR SOLVENTS; FINAL

    International Nuclear Information System (INIS)

    Benjamin J. McCoy; J.M. Smith

    1998-01-01

    This report outlines a distribution kinetics approach to macromolecular reactions that has been applied to several processes. The objective was to develop an understanding of high-temperature, dense-phase thermolytic processes for complex macromolecular systems, such as coal. Experiments and theory are described for chemical models that simulate depolymerization of coal. The approach has been exceptionally successful for the model macromolecular systems. Development of a novel chemical reaction engineering analysis, based on distribution kinetics, was a major accomplishment of the current research

  10. Purification of free hydrogen or hydrogen combined in a gaseous mixture by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Caron-Charles, M.; Gilot, B.

    1989-01-01

    Within the framework of the European fusion program, the authors are dealing with the tritium technology aspect. Hydrogen, free or under a combined form within a H 2 , N 2 , NH 3 , O 2 , gaseous mixture, can be purified by chemical reactions with uranium metal. The resulting reactions consist in absorbing the impurities without holding back H 2 . Working conditions have been defined according to two main goals: the formation of stable solid products, especially under hydrogenated atmosphere and the optimization of the material quantities to be used. Thermodynamical considerations have shown that the 950-1300 K temperature range should be suitable for this chemical process. Experiments performed with massive uranium set in a closed reactor at 973 K, have produced hydrogen according to the predicted reactions rates. But they have also pointed out the importance of interferences that might occur in the uranium-gas system, on the gases conversion rates. The comparison between the chemical kinetic ratings of the reactions of pure gases and the chemical kinetic ratings of the reactions of the same gases in mixture, has been set up. It proves that simultaneous reactions can modify the working conditions of the solid products formation, and particularly modify their structure. In this case, chemical kinetic ratings are increased up to their maximal value; that means surface phenomena are favoured as with uranium powder gases reactions. (orig.)

  11. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.

    1992-04-07

    The ultimate objective of this research has been to uncover novel reagents and experimental conditions for heteroatom removal and hydrogen transfer processes, which would be applicable to the liquefaction of coal under low-severity conditions. To this end, one phase of this research has investigated the cleavage of carbon-heteroatom bonds involving sulfur, oxygen, nitrogen and halogen by subvalent transition-metal complexes. A second phase of the study has assessed the capability of the same transition-metal complexes or of organoaluminum Lewis acids to catalyze the cleavage of carbon-hydrogen bonds in aromatics and hence to promote hydrogen shuttling. Finally, a third phase of our work has uncovered a remarkable synergistic effect of combinations of transition metals with organoaluminum Lewis acids on hydrogen shuttling between aromatics and hydroaromatics. (VC)

  12. Applications of heavy-ion reactions on hydrogen isotopes

    International Nuclear Information System (INIS)

    Evers, E.J.

    1987-01-01

    This thesis describes various aspects of 'inverse' reactions between the lightest nuclides, hydrogen and deuterium, and heavy ions in the range from carbon to phosphorus. The reactions studied in this thesis always result in one light ejectile and one excited heavy nucleus. Coincidence experiments have been performed in which both the emitted light particle and the gamma radiation emitted by the excited heavy nucleus produced, are detected. Ch. 1 describes the system built for the acquisition of data obtained in such coincidence experiments. Ch. 2 describes precision measurements of nuclear lifetimes and stopping powers. Coincident Doppler shift attenuation (DSA) experiments were performed with the reaction 2 H( 31 P,pγ) 32 P at E( 31 P 7+ )=50 MeV and thin Ti 2 H targets on Au, Ag and Cu backings. Mean lifetimes of the E x =513, 1150, 1323 and 1755 levels were determined with experimental stopping powers of Forster et al. These lifetimes were used as input in further analysis of the experimental data and of an additional experiment with a target on Mg backing to determine a consistent set of stopping power data for P ions with a velocity in the range 0-8(c/137) in the four materials mentioned. Ch.'s 3 and 4 deal with narrow resonances in reactions of nitrogen and fluorine beams with hydrogen targets. In Ch. 3 a method is described for the calibration of analyzing-magnet systems of heavy-ions accelerators. Ch. 4 describes an experiment to investigate the hydrogen concentration in silicon nitride films using a resonant inverse nuclear reaction. This method turns out to be a very suitable one for determining hydrogen concentration profiles with a good depth resolution over a large depth. 69 refs.; 23 figs.; 7 tabs

  13. Competitive reaction in hydrodenitrogenation and hydrodeoxygenation of coal-derived naphtha

    Energy Technology Data Exchange (ETDEWEB)

    Machida, M. (Idemitsu Kosan Co. Ltd., Tokyo (Japan). Central Research Lab.); Sakao, Y.; Ono, S. (Idemitsu Kosan Co. Ltd., Tokyo (Japan))

    1994-03-01

    The naphtha fraction derived from coal is expected to be one of the most suitable blending stocks for motor gasoline because of its high contents of cyclic hydrocarbons. However, since the contents of nitrogen and oxygen are high in the coal naphtha, the amounts of these elements must be reduced to acceptable levels. In this study, aiming to clarify the hydrodenitrogenation (HDN) and hydrodeoxygenation (HDO) performances of practical feed stocks, HDN and HDO of coal-derived naphtha and its model compounds were examined by using a catalyst Ni-Mo/Al2O3 group. There are tree types of nitrogen compounds, pyridine, pyrrole and aniline, in the coal-derived naphtha. Aniline type nitrogen compounds in the coal-derived naphtha are more resistant to HDN than pyridine type compounds, though aniline is more reactive than pyridine when the reaction is carried out individually. 14 refs., 7 figs., 3 tabs.

  14. Long-Term Demonstration of Hydrogen Production from Coal at Elevated Temperatures Year 6 - Activity 1.12 - Development of a National Center for Hydrogen Technology

    Energy Technology Data Exchange (ETDEWEB)

    Stanislowski, Joshua; Tolbert, Scott; Curran, Tyler; Swanson, Michael

    2012-04-30

    The Energy & Environmental Research Center (EERC) has continued the work of the National Center for Hydrogen Technology® (NCHT®) Program Year 6 Task 1.12 project to expose hydrogen separation membranes to coal-derived syngas. In this follow-on project, the EERC has exposed two membranes to coal-derived syngas produced in the pilot-scale transport reactor development unit (TRDU). Western Research Institute (WRI), with funding from the State of Wyoming Clean Coal Technology Program and the North Dakota Industrial Commission, contracted with the EERC to conduct testing of WRI’s coal-upgrading/gasification technology for subbituminous and lignite coals in the EERC’s TRDU. This gasifier fires nominally 200–500 lb/hour of fuel and is the pilot-scale version of the full-scale gasifier currently being constructed in Kemper County, Mississippi. A slipstream of the syngas was used to demonstrate warm-gas cleanup and hydrogen separation using membrane technology. Two membranes were exposed to coal-derived syngas, and the impact of coal-derived impurities was evaluated. This report summarizes the performance of WRI’s patent-pending coalupgrading/ gasification technology in the EERC’s TRDU and presents the results of the warm-gas cleanup and hydrogen separation tests. Overall, the WRI coal-upgrading/gasification technology was shown to produce a syngas significantly lower in CO2 content and significantly higher in CO content than syngas produced from the raw fuels. Warm-gas cleanup technologies were shown to be capable of reducing sulfur in the syngas to 1 ppm. Each of the membranes tested was able to produce at least 2 lb/day of hydrogen from coal-derived syngas.

  15. Reaction-diffusion modeling of hydrogen in beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Wensing, Mirko; Matveev, Dmitry; Linsmeier, Christian [Forschungszentrum Juelich GmbH, Institut fuer Energie- und Klimaforschung - Plasmaphysik (Germany)

    2016-07-01

    Beryllium will be used as first-wall material for the future fusion reactor ITER as well as in the breeding blanket of DEMO. In both cases it is important to understand the mechanisms of hydrogen retention in beryllium. In earlier experiments with beryllium low-energy binding states of hydrogen were observed by thermal desorption spectroscopy (TDS) which are not yet well understood. Two candidates for these states are considered: beryllium-hydride phases within the bulk and surface effects. The retention of deuterium in beryllium is studied by a reaction rate approach using a coupled reaction diffusion system (CRDS)-model relying on ab initio data from density functional theory calculations (DFT). In this contribution we try to assess the influence of surface recombination.

  16. A study of thermal reactions of coal with polyamides

    Czech Academy of Sciences Publication Activity Database

    Straka, Pavel; Náhunková, Jana

    2004-01-01

    Roč. 1, č. 2 (2004), s. 239-243 ISSN 1211-1910 R&D Projects: GA AV ČR IAA2046902 Institutional research plan: CEZ:AV0Z3046908 Keywords : coal * kinetics * polyamides Subject RIV: CD - Macromolecular Chemistry

  17. Use of Heterogenized Metal Complexes in Hydrogenation Reactions: Comparison of Hydrogenation and CTH Reactions.

    Czech Academy of Sciences Publication Activity Database

    Bata, P.; Zsigmond, A.; Gyémánt, M.; Czeglédi, A.; Klusoň, Petr

    2015-01-01

    Roč. 41, č. 12 (2015), s. 9281-9294 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Castle Trest, 16.09.2014-20.09.2014] Institutional support: RVO:67985858 Keywords : catalytic transfer hydrogenation * iron-phthalocyanine catalyst * chemoselectivity Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

  18. Report on the research achievements in the Sunshine Project in fiscal 1992. Studies on liquefying reaction in coal, and reforming and utilization of the products; 1992 nendo sekitan no ekika hanno to seiseibutsu no kaishitsu riyo no kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1983-03-01

    This paper describes the achievements in the Sunshine Project in fiscal 1992 in studies on liquefying reaction in coal, and reforming of the products. High conversion rate was attained in the co-treatment of bitumen and Taiheiyo coals by using highly dispersing oil soluble solvent without performing coking, even if the asphaltene concentration is high. When a very highly acidic trifluoromethane sulfonic acid catalyst is used, hydrogenation and conversion to solubilized low molecules is possible even with a solvent having low affinity with coal. Swelling effect by tetralin is remarkable in pulverized coal, and the conversion rate was improved greatly under high-pressure hydrogen. When naphtha of the Wandoan coal liquefied oil is given extraction treatment with base and acid/base, the gas production decreases noticeably when hydrogenating and refining the extracts, resulting in reduced hydrogen consumption and improved oil recovery rate. Furthermore, when the extraction treated naphtha is hydrogenated, denitrification can be achieved completely. Kerosene and light oil liquefied from the Wandoan coal were cracked by fluidity contact, whereas the light gravity product yield due to the decomposition was found low because of containing a great amount of two-ring aromatics. The pressure crystal deposition method using solvent is effective in separation of high-melting point compounds including anthracene from heavy gravity oil. (NEDO)

  19. Determination of Se at low concentration in coal by collision/reaction cell technology inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Henn, Alessandra S.; Rondan, Filipe S.; Mesko, Marcia F.; Mello, Paola A.; Perez, Magali; Armstrong, Joseph; Bullock, Liam A.; Parnell, John; Feldmann, Joerg; Flores, Erico M. M.

    2018-05-01

    A method is proposed for the determination of selenium at low concentration in coal by collision/reaction cell technology inductively coupled plasma mass spectrometry (CRC-ICP-MS). Samples were decomposed by high pressure microwave-assisted wet digestion (MAWD) using 250 mg of coal, a mixture of 5 mL of 14.4 mol L-1 HNO3 and 1 mL of 40% HF and 70 min of heating program (200 °C and 40 bar). Hydrogen gas used in the collision/reaction cell was investigated to minimize the argon-based interferences at m/z 77, 78 and 80. The rejection parameter (RPq) and the H2 gas flow rate were set to 0.45 and 4.8 mL min-1, respectively. The use of H2 in the cell resulted in other polyatomic interferences, such as 76Ge1H+, 79Br1H+ and 81Br1H+, which impaired Se determination using 77Se, 80Se and 82Se isotopes, thus Se determination was carried out by monitoring only 78Se isotope. Selenium was determined in certified reference materials of coal (NIST 1635 and SARM 20) and an agreement better than 95% was observed between the results obtained by CRC-ICP-MS and the certified values. Under optimized conditions, the instrumental limit of detection was 0.01 μg L-1 and the method limit of detection was 0.01 μg g-1, which was suitable for Se determination at very low concentration in coal.

  20. Elucidation of hydrogen mobility in tetralin under coal liquefaction conditions using a tritium tracer method. Effects of the addition of H2S and H2O; Tritium tracer ho wo mochiita sekitan ekika hanno jokenka deno tetralin no suiso idosei hyoka. Ryuka suiso oyobi mizu no tenka koka

    Energy Technology Data Exchange (ETDEWEB)

    Kanbe, M.; Saito, M.; Ishihara, A.; Kabe, T. [Tokyo University of Agriculture and Technology, Tokyo (Japan)

    1996-10-28

    It was previously reported that the tritium tracer method is useful for the quantitative consideration of hydrogen behavior in coal during coal liquefaction reaction. Tetralin is excellent hydrogen donating solvent, and is considered as one of the model compounds of coal. In this study, effects of H2S and H2O on the hydrogen exchange reaction between tetralin and gaseous hydrogen labeled by tritium were investigated. It was suggested that the conversion of tetralin and the hydrogen exchange reaction between gaseous hydrogen and tetralin proceed through the radical reaction mechanism with a tetralyl radical as an intermediate product. When H2S existed in this reaction, the hydrogen exchange yield increased drastically without changing the conversion yield. This suggested that the hydrogen exchange reaction proceeds even in the reaction where radical does not give any effect. In the case of H2O addition, the conversion yield and hydrogen exchange rate decreased into a half or one-third. It was suggested that H2O inhibited the formation process of tetralyl radical. 6 refs., 4 figs.

  1. Hydrogen desorption reactions of Li-N-H hydrogen storage system: Estimation of activation free energy

    International Nuclear Information System (INIS)

    Matsumoto, Mitsuru; Haga, Tetsuya; Kawai, Yasuaki; Kojima, Yoshitsugu

    2007-01-01

    The dehydrogenation reactions of the mixtures of lithium amide (LiNH 2 ) and lithium hydride (LiH) were studied under an Ar atmosphere by means of temperature programmed desorption (TPD) technique. The dehydrogenation reaction of the LiNH 2 /LiH mixture was accelerated by addition of 1 mol% Ti(III) species (k = 3.1 x 10 -4 s -1 at 493 K), and prolonged ball-milling time (16 h) further enhanced reaction rate (k = 1.1 x 10 -3 s -1 at 493 K). For the hydrogen desorption reaction of Ti(III) doped samples, the activation energies estimated by Kissinger plot (95 kJ mol -1 ) and Arrhenius plot (110 kJ mol -1 ) were in reasonable agreement. The LiNH 2 /LiH mixture without Ti(III) species, exhibited slower hydrogen desorption process and the kinetic traces deviated from single exponential behavior. The results indicated the Ti(III) additives change the hydrogen desorption reaction mechanism of the LiNH 2 /LiH mixture

  2. Thermal relaxation of bituminous coal to improve donation ability of hydrogen radicals in flash pyrolysis; Sekitan kozo kanwa ni yoru suiso radical kyoyo noryoku no kojo wo mezashita netsubunkai mae shori

    Energy Technology Data Exchange (ETDEWEB)

    Mori, T.; Isoda, T.; Kusakabe, K.; Morooka, S. [Kyushu University, Fukuoka (Japan). Faculty of Engineering; Hayashi, J. [Hokkaido University, Sapporo (Japan). Center for Advanced Research of Energy Technology

    1996-10-28

    In terms of coal conversion reaction, the behavior of bituminous coal heated beyond a glass transition point was examined on the basis of pyrolyzed products, and the effect of an increase in proton mobility on promotion of coal decomposition was evaluated. In experiment, after Illinois bituminous coal specimen was heated up to a specific temperature in N2 or He gas flow at a rate of 5K/min, the specimen was directly transferred to a pyrolyzer for instantaneous pyrolysis. As the experimental result, the glass transition temperature of the Illinois coal specimen was calculated to be 589K from a differential scanning calorimetry (DSC) profile. From the pyrolysis result of the Illinois coal specimen heated up to 623K, the char yield decreased by 3kg as compared with that of the original coal, while the tar yield increased by 4kg up to 27kg per 100kg of the original coal. This tar increase was larger than that of cooled coal. These results suggested that the donation of hydrogen radicals to coal fragments is improved with an increase in proton mobility. 4 refs., 4 figs., 1 tab.

  3. Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals

    DEFF Research Database (Denmark)

    Knap, Hasse Christian; Jørgensen, Solvejg

    2017-01-01

    -shift with X = 6, 7, 8, or 9) in the hydroperoxy acyl peroxy radicals, this H-shift is a reversible reaction and it scrambles between two peroxides, hydroperoxy acyl peroxy and peroxy peroxoic acid radicals. The forward reaction rate constants of the 1,X-OOH H-shift reactions are estimated to be above 103 s–1...... with transition state theory corrected with Eckart quantum tunnelling correction. The ratio between the forward and reverse reaction rate constant of the 1,X-OOH H-shift reactions is around ∼105. Therefore, the equilibrium is pushed toward the production of peroxy peroxoic acid radicals. These very fast 1,X-OOH H......We have used quantum mechanical chemical calculations (CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/aug-cc-pVTZ) to investigate the hydrogen shift (H-shift) reactions in acyl peroxy and hydroperoxy acyl peroxy radicals. We have focused on the H-shift reactions from a hydroperoxy group (OOH) (1,X-OOH H...

  4. Reaction path sampling of the reaction between iron(II) and hydrogen peroxide in aqueous solution

    NARCIS (Netherlands)

    Ensing, B.; Baerends, E.J.

    2002-01-01

    Previously, we have studied the coordination and dissociation of hydrogen peroxide with iron(II) in aqueous solution by Car-Parrinello molecular dynamics at room temperature. We presented a few illustrative reaction events, in which the ferryl ion ([Fe(IV)O

  5. Study of initial stage in coal liquefaction. Increase in oil yield with suppression of retrogressive reaction during initial stage; Ekika hanno no shoki katei ni kansuru kenkyu. 1.

    Energy Technology Data Exchange (ETDEWEB)

    Uesugi, K.; Kanaji, M.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

    1996-10-28

    For the coal liquefaction, improvement of liquefaction conditions and increase of liquefied oil yield are expected by suppressing the recombination through rapid stabilization of pyrolytic radicals which are formed at the initial stage of liquefaction. Two-stage liquefaction combining prethermal treatment and liquefaction was performed under various conditions, to investigate the effects of reaction conditions on the yields and properties of products as well as to increase liquefied oil yield. Consequently, it was found that the catalyst contributes greatly to the hydrogen transfer to coal at the prethermal treatment. High yield of n-hexane soluble fraction with products having low condensation degree could be obtained by combining the prethermal treatment in the presence of hydrogen and catalyst with the concentration of slurry after the treatment. This was considered to be caused by the synergetic effect between the improvement of liquefaction by suppressing polymerization/condensation at the initial stage of reaction through the prethermal treatment and the effective hydrogen transfer accompanied with the improvement of contact efficiency of coal/catalyst by the concentration of slurry at the stage of liquefaction. 4 refs., 8 figs.

  6. Effect of reaction temperature on the PM10 features during coal combustion

    International Nuclear Information System (INIS)

    Sui, J.C.; Du, Y.G.; Liu, Q.C.

    2008-01-01

    Coal-fired power plants produce fine fly ash consisting of particulate matter (PM). Particulate matter less than 10 micrometers in aerodynamic diameter (PM 1 0) is of significant concern because of its adverse environmental and health impacts. This paper studied the effect of reaction temperature on particulate matter (PM 1 0) emission and its chemical composition. The emission characteristics and elemental partition of PM 1 0 from coal combustion were investigated in a drop tube furnace. The paper discussed the experimental apparatus and conditions as well as the coal properties and sample analysis. Liupanshui (LPS) bituminous coal from China was used for the study. The fuel composition of LPS coal and the composition of low temperature ash of Chinese LPS coal were described. The paper also presented the results of the study with reference to particle size distribution and emission characteristic of PM 1 0; elemental partition within PM 1 0; and effect of the reaction temperature on elemental partition within PM 1 0. The PM mass size distribution was found to be bimodal. 14 refs., 2 tabs., 6 figs

  7. Signatures of a quantum diffusion limited hydrogen atom tunneling reaction.

    Science.gov (United States)

    Balabanoff, Morgan E; Ruzi, Mahmut; Anderson, David T

    2017-12-20

    We are studying the details of hydrogen atom (H atom) quantum diffusion in highly enriched parahydrogen (pH 2 ) quantum solids doped with chemical species in an effort to better understand H atom transport and reactivity under these conditions. In this work we present kinetic studies of the 193 nm photo-induced chemistry of methanol (CH 3 OH) isolated in solid pH 2 . Short-term irradiation of CH 3 OH at 1.8 K readily produces CH 2 O and CO which we detect using FTIR spectroscopy. The in situ photochemistry also produces CH 3 O and H atoms which we can infer from the post-photolysis reaction kinetics that display significant CH 2 OH growth. The CH 2 OH growth kinetics indicate at least three separate tunneling reactions contribute; (i) reactions of photoproduced CH 3 O with the pH 2 host, (ii) H atom reactions with the CH 2 O photofragment, and (iii) long-range migration of H atoms and reaction with CH 3 OH. We assign the rapid CH 2 OH growth to the following CH 3 O + H 2 → CH 3 OH + H → CH 2 OH + H 2 two-step sequential tunneling mechanism by conducting analogous kinetic measurements using deuterated methanol (CD 3 OD). By performing photolysis experiments at 1.8 and 4.3 K, we show the post-photolysis reaction kinetics change qualitatively over this small temperature range. We use this qualitative change in the reaction kinetics with temperature to identify reactions that are quantum diffusion limited. While these results are specific to the conditions that exist in pH 2 quantum solids, they have direct implications on the analogous low temperature H atom tunneling reactions that occur on metal surfaces and on interstellar grains.

  8. Advanced gasifier and water gas shift technologies for low cost coal conversion to high hydrogen syngas

    Energy Technology Data Exchange (ETDEWEB)

    Kramer, Andrew Kramer [Gas Technology Inst., Des Plaines, IL (United States)

    2016-09-30

    The Gas Technology Institute (GTI) and team members RTI International (RTI), Coanda Research and Development, and Nexant, are developing and maturing a portfolio of technologies to meet the United States Department of Energy (DOE) goals for lowering the cost of producing high hydrogen syngas from coal for use in carbon capture power and coal-to-liquids/chemicals. This project matured an advanced pilot-scale gasifier, with scalable and commercially traceable components, to readiness for use in a first-of-a-kind commercially-relevant demonstration plant on the scale of 500-1,000 tons per day (TPD). This was accomplished through cold flow simulation of the gasifier quench zone transition region at Coanda and through an extensive hotfire gasifier test program on highly reactive coal and high ash/high ash fusion temperature coals at GTI. RTI matured an advanced water gas shift process and catalyst to readiness for testing at pilot plant scale through catalyst development and testing, and development of a preliminary design basis for a pilot scale reactor demonstrating the catalyst. A techno-economic analysis was performed by Nexant to assess the potential benefits of the gasifier and catalyst technologies in the context of power production and methanol production. This analysis showed an 18%reduction in cost of power and a 19%reduction in cost of methanol relative to DOE reference baseline cases.

  9. Two dimensional simulation of hydrogen iodide decomposition reaction using fluent code for hydrogen production using nuclear technology

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Jung Sik [The Institute of Machinery and Electronic Technology, Mokpo National Maritime University, Mokpo (Korea, Republic of); Shin, Young Joon; Lee, Ki Young [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Choi, Jae Hyuk [Division of Marine Engineering System, Korea Maritime and Ocean University, Busan (Korea, Republic of)

    2015-06-15

    The operating characteristics of hydrogen iodide (HI) decomposition for hydrogen production were investigated using the commercial computational fluid dynamics code, and various factors, such as hydrogen production, heat of reaction, and temperature distribution, were studied to compare device performance with that expected for device development. Hydrogen production increased with an increase of the surface-to-volume (STV) ratio. With an increase of hydrogen production, the reaction heat increased. The internal pressure and velocity of the HI decomposer were estimated through pressure drop and reducing velocity from the preheating zone. The mass of H2O was independent of the STV ratio, whereas that of HI decreased with increasing STV ratio.

  10. Facile Hydrogen Evolution Reaction on WO3Nanorods

    Directory of Open Access Journals (Sweden)

    Rajeswari Janarthanan

    2007-01-01

    Full Text Available AbstractTungsten trioxide nanorods have been generated by the thermal decomposition (450 °C of tetrabutylammonium decatungstate. The synthesized tungsten trioxide (WO3 nanorods have been characterized by XRD, Raman, SEM, TEM, HRTEM and cyclic voltammetry. High resolution transmission electron microscopy and X-ray diffraction analysis showed that the synthesized WO3nanorods are crystalline in nature with monoclinic structure. The electrochemical experiments showed that they constitute a better electrocatalytic system for hydrogen evolution reaction in acid medium compared to their bulk counterpart.

  11. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

    2015-12-31

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  12. Rydberg phases of Hydrogen and low energy nuclear reactions

    Science.gov (United States)

    Olafsson, Sveinn; Holmlid, Leif

    2016-03-01

    For over the last 26 years the science of cold fusion/LENR has been researched around the world with slow pace of progress. Modest quantity of excess heat and signatures of nuclear transmutation and helium production have been confirmed in experiments and theoretical work has only resulted in a large flora of inadequate theoretical scenarios. Here we review current state of research in Rydberg matter of Hydrogen that is showing strong signature of nuclear processes. In the presentation experimental behavior of Rydberg matter of hydrogen is described. An extensive collaboration effort of surface physics, catalysis, atomic physics, solid state physics, nuclear physics and quantum information is need to tackle the surprising experimental results that have so far been obtained. Rydberg matter of Hydrogen is the only known state of matter that is able to bring huge collection of protons to so short distances and for so long time that tunneling becomes a reasonable process for making low energy nuclear reactions. Nuclear quantum entanglement can also become realistic process at theses conditions.

  13. Influence of reaction parameters on brown coal-polyolefinic plastic co-pyrolysis behavior

    Energy Technology Data Exchange (ETDEWEB)

    Sharypov, V.I.; Beregovtsova, N.G.; Kuznetsov, B.N. [Institute of Chemistry and Chemical Technology SB RAS, K.Marx Str. 42, 660049 Krasnoyarsk (Russian Federation); Cebolla, V.L. [Instituto de Carboquimica, CSIC, Miguel Luesma, 4, 50015 Zaragoza (Spain); Collura, S.; Finqueneisel, G.; Zimny, T.; Weber, J.V. [Laboratoire de Chimie et Applications, Universite de Metz, rue V.Demange, 57500 Saint-Avold (France)

    2007-03-15

    Co-processing of polyolefinic polymers with Kansk-Achinsk (Russia) brown coal was investigated by thermogravimetry (TG) and autoclave pyrolysis under argon and hydrogen pressure in catalytic conditions (or not). Gas chromatography-mass spectrometry (GC-MS) and high performance thin layer chromatography (HPTLC) were used to analyze the distillate products. Some synergistic effects indicate chemical interaction between the products of thermal decomposition of coal and plastic. In co-pyrolysis under H{sub 2} a significant increasing of coal conversion degree as a function of polymer amount in feedstock was found. Simultaneously the coal promoted formation of distillate products from polymers. Some alkyl aromatic and O-containing substances were detected in co-pyrolysis fraction boiling in the range 180-350 C, indicating interactions between coal and plastic. Iron containing ore materials, modified by mechanochemical treatment, demonstrated a catalytic activity in hydropyrolysis process. In catalytic conditions, increases of the mixtures conversion degree by 9-13 wt.%, of distillate fraction yields by 1.2-1.6 times and a decrease of olefins and polycyclic components were observed. (author)

  14. Coal

    International Nuclear Information System (INIS)

    Teissie, J.; Bourgogne, D. de; Bautin, F.

    2001-12-01

    Coal world production represents 3.5 billions of tons, plus 900 millions of tons of lignite. 50% of coal is used for power generation, 16% by steel making industry, 5% by cement plants, and 29% for space heating and by other industries like carbo-chemistry. Coal reserves are enormous, about 1000 billions of tons (i.e. 250 years of consumption with the present day rate) but their exploitation will be in competition with less costly and less polluting energy sources. This documents treats of all aspects of coal: origin, composition, calorific value, classification, resources, reserves, production, international trade, sectoral consumption, cost, retail price, safety aspects of coal mining, environmental impacts (solid and gaseous effluents), different technologies of coal-fired power plants and their relative efficiency, alternative solutions for the recovery of coal energy (fuel cells, liquefaction). (J.S.)

  15. Sorption Enhanced Reaction Process (SERP) for production of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Anand, M.; Hufton, J.; Mayorga, S. [Air Products and Chemicals, Inc., Allentown, PA (United States)] [and others

    1996-10-01

    Sorption Enhanced Reaction Process (SERP) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The key consequences of SERP are: (i) reformation reaction is carried out at a significantly lower temperature (300-500{degrees}C) than that in a conventional SMR reactor (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (ii) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 98+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (iii) downstream hydrogen purification step is either eliminated or significantly reduced in size. The first phase of the program has focused on the development of a sorbent for CO{sub 2} which has (a) reversible CO{sub 2} capacity >0.3 mmol/g at low partial pressures of CO{sub 2} (0.1 - 1.0 atm) in the presence of excess steam (pH{sub 2}O/pCO{sub 2}>20) at 400-500{degrees}C and (b) fast sorption-desorption kinetics for CO{sub 2}, at 400-500{degrees}C. Several families of supported sorbents have been identified that meet the target CO{sub 2} capacity. A few of these sorbents have been tested under repeated sorption/desorption cycles and extended exposure to high pressure steam at 400-500{degrees}C. One sorbent has been scaled up to larger quantities (2-3 kg) and tested in the laboratory process equipment for sorption and desorption kinetics of CO{sub 2}. The CO{sub 2}, sorption and desorption kinetics are desirably fast. This was a critical path item for the first phase of the program and now has been successfully demonstrated. A reactor has been designed that will allow nearly isothermal operation for SERP-SMR. This reactor was integrated into an overall process flow diagram for the SERP-SMR process.

  16. Modeling of Syngas Reactions and Hydrogen Generation Over Sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Kamil Klier; Jeffery A. Spirko; Michael L. Neiman

    2002-09-17

    The objective of the research is to analyze pathways of reactions of hydrogen with oxides of carbon over sulfides, and to predict which characteristics of the sulfide catalyst (nature of metal, defect structure) give rise to the lowest barriers toward oxygenated hydrocarbon product. Reversal of these pathways entails the generation of hydrogen, which is also proposed for study. In this first year of study, adsorption reactions of H atoms and H{sub 2} molecules with MoS{sub 2}, both in molecular and solid form, have been modeled using high-level density functional theory. The geometries and strengths of the adsorption sites are described and the methods used in the study are described. An exposed MO{sup IV} species modeled as a bent MoS{sub 2} molecule is capable of homopolar dissociative chemisorption of H{sub 2} into a dihydride S{sub 2}MoH{sub 2}. Among the periodic edge structures of hexagonal MoS{sub 2}, the (1{bar 2}11) edge is most stable but still capable of dissociating H{sub 2}, while the basal plane (0001) is not. A challenging task of theoretically accounting for weak bonding of MoS{sub 2} sheets across the Van der Waals gap has been addressed, resulting in a weak attraction of 0.028 eV/MoS{sub 2} unit, compared to the experimental value of 0.013 eV/MoS{sub 2} unit.

  17. Intrinsic reaction kinetics of coal char combustion by direct measurement of ignition temperature

    International Nuclear Information System (INIS)

    Kim, Ryang-Gyoon; Jeon, Chung-Hwan

    2014-01-01

    A wire heating reactor that can use a synchronized experimental method was developed to obtain the intrinsic kinetics of large coal char particles ranging in size from 0.4 to 1 mm. This synchronization system consists of three parts: a thermocouple wire for both heating and direct measurement of the particle temperature, a photodetector sensor for determining ignition/burnout points by measuring the intensity of luminous emission from burning particles, and a high-speed camera–long-distance microscope for observing and recording the movement of luminous zone directly. Coal char ignition was found to begin at a spot on the particle's external surface and then moved across the entire particle. Moreover, the ignition point determined according to the minimum of dT/dt is a spot point and not a full growth point. The ignition temperature of the spot point rises as the particle diameter increases. A spot ignition model, which describes the ignition in terms of the internal conduction and external/internal oxygen diffusion, was then developed to evaluate the intrinsic kinetics and predict the ignition temperature of the coal char. Internal conduction was found to be important in large coal char particles because its effect becomes greater than that of oxygen diffusion as the particle diameter increases. In addition, the intrinsic kinetics of coal char obtained from the spot ignition model for two types of coal does not differ significantly from the results of previous investigators. -- Highlights: • A novel technique was used to measure the coal char particle temperature. • The ignition point determined from a dT/dt minimum is a spot ignition point. • A spot ignition model was suggested to analyze the intrinsic reaction kinetics of coal char. • Internal conduction has to be considered in order to evaluate the intrinsic kinetics for larger particle (above 1 mm)

  18. Cathodic over-potential and hydrogen partial pressure coupling in hydrogen evolution reaction of marine steel under hydrostatic pressure

    International Nuclear Information System (INIS)

    Xiong, X.L.; Zhou, Q.J.; Li, J.X.; Volinsky, Alex A.; Su, Y.J.

    2017-01-01

    Highlights: •Hydrostatic pressure increases the Volmer and the Heyrovsky reactions rates. •Hydrostatic pressure decreases the Tafel reaction rate. •Hydrogen adsorption conditions change with pressure under −1.2 and −1.3 V SSE . •Under −1.2 and −1.3 V SSE , the Heyrovsky reaction dominates the hydrogen recombination. •Under −1.0 and −1.1 V SSE , the Tafel reaction dominates the hydrogen recombination. -- Abstract: A new electrochemical impedance spectroscopy (EIS) model, which considers both the Tafel recombination and the Heyrovsky reaction under permeable boundary conditions, was developed to characterize the kinetic parameters of the hydrogen evolution reaction (HER) under hydrostatic pressure. The effect of the hydrostatic pressure on the kinetic parameters of the HER and the permeation of A514 steel in alkaline solution were measured using potentiodynamic polarization, the Devanathan cell hydrogen permeation, and EIS. The hydrostatic pressure accelerates the Volmer reaction and inhibits the Tafel recombination, which increases the number of adsorbed hydrogen atoms. On the other hand, the pressure accelerates the Heyrovsky reaction, which decreases the amount of adsorbed hydrogen atoms. At 10 to 40 MPa hydrostatic pressure within the −1.0 to −1.1 V SSE cathodic potential region, the HER is controlled by hydrogen partial pressure, and hydrogen adsorption is the Langmuir type. Within the −1.2 to −1.3 V SSE cathodic potential region, the HER is controlled by the potential, and hydrogen adsorption gradually transfers from the Langmuir type to the Temkin type with increasing hydrostatic pressure.

  19. Conceptual study of hydrogen donor solvent in the NEDOL coal liquefaction process

    Energy Technology Data Exchange (ETDEWEB)

    Kouzu, M.; Onozaki, M.; Oi, S. [Mitsui SRC Co Ltd, Tokyo (Japan)

    2002-03-01

    A 150 ton/day coal liquefaction pilot plant (PP) of the NEDOL process, supported by New Energy and Industrial Technology Development Organization (NEDO), was operated successfully for a total of 269 days at Kashima, Japan. With a great number of data obtained through the operation, the design procedure for the NEDOL process was studied. Middle and heavy oils from the coal employed were recycled as a hydrogen-donor solvent after hydrotreatment over Ni Mo/gamma-Al2O{sub 3} in a trickle bed reactor. The hydrogen donating ability of the solvent was high enough to obtain higher oil yield (50-58 wt%) at the aromaticity of ca. 0.45. Life expectancy of solvent hydrotreatment catalyst, requisite to the hydrotreater design, was estimated under PP operating conditions. In addition, physical properties of the solvent required for process design were determined, and hydrodynamics in the liquefaction bubble column reactors were examined. Taking the obtained hydrodynamics and thermal behavior into consideration, a design procedure of the liquefaction bubble column reactors was establsihed using a process simulator (CARD) validated by the product yields of PP. The simulation including distillation and solvent hydrotreatment showed that the content of heavy oil fraction (b.p. 350 - 538{degree} C) in the solvent was a determinant factor in the design of a large scale plant based on the NEDOL process.

  20. Coal tar phototoxicity: characteristics of the smarting reaction

    International Nuclear Information System (INIS)

    Diette, K.M.; Gange, R.W.; Stern, R.S.; Arndt, K.A.; Parrish, J.A.

    1985-01-01

    The properties and ultraviolet exposure parameters of tar smarts were examined in an effort to elucidate the mechanisms involved. It was show that irradiation with 1 minimal smarting dose (MSD) of UVA immediately following tar removal lowered the MSD for 6 h, demonstrated by subsequent challenge with UVA. Following 3 MSDs this memory effect was demonstrable for 24 h. The smarting reaction was area dependent--smaller areas of exposure require higher doses of UVA to induce smarting. Smarting followed reciprocity over a 6-fold range of irradiances (2-12.5 mW/cm2) but higher irradiances required higher doses of UVA, perhaps due to a delay in the recognition and reporting of smarting. The smarting reaction and delayed erythema due to UVA and tar were equally blocked by sunscreen

  1. Research on mechanism of and catalysts for extraction liquefaction of coal using coal-based solvents; Sekitankei yozai ni yoru sekitan no chushutsu ekika kiko to shokubai no kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1981-07-01

    Papers of Professor Yoshio Kamiya of Tokyo University are compiled into this report. The list of the papers includes (1) Synthesis of heavy fuel oils from coal; (2) Research and development of coal liquefaction; (3) Dissolution reaction of coal by hydrogen-donating aromatic solvents (I); (4) Effect of hydrogen-donor solvent on the liquefaction of coal; (5) Recent studies on the chemical structure of solvent refined coal; (6) Dissolution reaction of coal by hydrogen-donating aromatic solvents (II); (7) Future of coal as energy material; (8), (9), (10) same as (6) in the subject discussed; (11) Recent studies on coal liquefaction catalysts; (12) Environmental problems and drain treatment to accompany processes of converting fossil resources into fuels; (13) Chemistry of coal oxidation; (14) Fractionation and analysis of solvent refined coal by gel permeation chromatography; (15) Current state of research and development of coal liquefaction; (16) Properties and components of coal oils from coal liquefaction processes under development; (17) Solvent effect of coal derived aromatic compounds on the liquefaction of Akabira coal; (18) Chemistry of coal liquefaction; (19) Research and development of coal liquefaction in the U.S.; (20) Thermal treatment of coal-related aromatic ethers in tetralin solution; (21) Recent technology of utilizing heavy carbon resources; (22) Chemical properties and reactivity of coal; (23) Current state and future of development of coal liquefaction processes; and (24) Development of overseas coal liquefaction projects. (NEDO)

  2. Experimental evaluation of improved dual temperature hydrogen isotopic exchange reaction system

    International Nuclear Information System (INIS)

    Asakura, Yamato; Uchida, Shunsuke

    1984-01-01

    A proposed dual temperature hydrogen isotopic exchange reaction system between water and hydrogen gas is evaluated experimentally. The proposed system is composed of low temperature co-current reactors for reaction between water mists and hydrogen gas and high temperature co-current reactors for reaction between water vapor and hydrogen gas. Thus, operation is possible under atmospheric pressure with high reaction efficiency. Using the pilot test system which is composed of ten low temperature (30 0 C) reaction units and ten high temperature (200 0 C) reaction units, an experimental separation of deuterium from light water is carried out. The enrichment factor under steady state conditions, its dependency on operating time, and the reaction period necessary to obtain the steady state enrichment factor are determined experimentally and compared with calculations. It is shown that separation ability in a multistage reaction system can be estimated by numerical calculation using actual reaction efficiency in a unit reactor. (author)

  3. Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

    Science.gov (United States)

    Niyitanga, Theophile; Jeong, Hae Kyung

    2017-10-01

    Graphite oxide and molybdenum disulfide (GO-MoS2) composite is prepared through a wet process by using hydrolysis of ammonium tetrathiomolybdate, and it exhibits excellent catalytic activity of the hydrogen evolution reaction (HER) with a low overpotential of -0.47 V, which is almost two and three times lower than those of precursor MoS2 and GO. The high performance of HER of the composite attributes to the reduced GO supporting MoS2, providing a conducting network for fast electron transport from MoS2 to electrodes. The composite also shows high stability after 500 cycles, demonstrating a synergistic effect of MoS2 and GO for efficient HER.

  4. Impact of organic-mineral matter interactions on thermal reaction pathways for coal model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Buchanan, A.C. III; Britt, P.F.; Struss, J.A. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

    1995-07-01

    Coal is a complex, heterogeneous solid that includes interdispersed mineral matter. However, knowledge of organic-mineral matter interactions is embryonic, and the impact of these interactions on coal pyrolysis and liquefaction is incomplete. Clay minerals, for example, are known to be effective catalysts for organic reactions. Furthermore, clays such as montmorillonite have been proposed to be key catalysts in the thermal alteration of lignin into vitrinite during the coalification process. Recent studies by Hatcher and coworkers on the evolution of coalified woods using microscopy and NMR have led them to propose selective, acid-catalyzed, solid state reaction chemistry to account for retained structural integrity in the wood. However, the chemical feasibility of such reactions in relevant solids is difficult to demonstrate. The authors have begun a model compound study to gain a better molecular level understanding of the effects in the solid state of organic-mineral matter interactions relevant to both coal formation and processing. To satisfy the need for model compounds that remain nonvolatile solids at temperatures ranging to 450 C, model compounds are employed that are chemically bound to the surface of a fumed silica (Si-O-C{sub aryl}linkage). The organic structures currently under investigation are phenethyl phenyl ether (C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}OC{sub 6}H{sub 5}) derivatives, which serve as models for {beta}-alkyl aryl ether units that are present in lignin and lignitic coals. The solid-state chemistry of these materials at 200--450 C in the presence of interdispersed acid catalysts such as small particle size silica-aluminas and montmorillonite clay will be reported. Initial focus will be on defining the potential impact of these interactions on coal pyrolysis and liquefaction.

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

    Energy Technology Data Exchange (ETDEWEB)

    Barton, Tom [Western Research Inst. (WRI), Laramie, WY (United States)

    2013-09-01

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

  6. Report on the research achievements in the Sunshine Project in fiscal 1990. Studies on coal liquefying reaction, and reforming and utilization of the products; 1990 nendo sekitan no ekika hanno to seiseibutsu no kaishitsu riyo no kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1991-03-01

    This paper describes the achievements in the Sunshine Project in fiscal 1990 on research of coal liquefying reaction. The research contributes to developing a coal liquefaction technology as one of the methods for manufacturing clean energy and chemical raw materials from coal. In the fundamental study on the liquefaction, primarily liquefied heavy constituents in different types of coals were divided into such constituents as HI, TI, and THFI to discuss the performance and coking behavior of each constituent as solvent. Furthermore, effects of hydrogenation treatment were also elucidated. Decomposing reaction was performed on different heavy products to discuss effects of the reaction conditions. In the liquefying reaction using petroleum-based heavy oil as solvent, different shale oils were used in experiments for comparison with the case of using tar sand bitumen. In the study of reforming the product, comparison was carried out on reactions in hydrogenation treatment and contact decomposition of medium to heavy fractions of liquefied oil. A separation experiment was made on hetero compounds by means of solvent extraction and pressure crystallization of liquefied oil naphtha and light oil fraction. Effects of additive were investigated in an engine test on the stabilized and balanced light oil fraction. Discussions were given on high level utilization of heat treated oil recovered from residues in liquefaction distillation. (NEDO)

  7. Studies on the decomposition of ethyl diazoacetate and its reaction with coal. Formation of a new tetrameric product and reagent access within the coal

    Energy Technology Data Exchange (ETDEWEB)

    Pomerantz, M.; Rooney, P.

    A new tetrameric pyrazoline, 10, has been observed in the thermal and Fe/sub 2/O/sub 3/-catalyzed decomposition of ethyl diazoacetate (2) as well as when several coal samples were treated thermally with 2 under various conditions. Identification of 10 was based on spectral properties and an independent synthesis. A comparison of the amounts of diethyl fumarate (3), diethyl maleate (4), the trimeric pyrazoline 5, triethyl trans-cyclopropane-1,2,3-tricarboxylate (8), and the tetrameric pyrazoline 10 formed in the coal reactions with the relative quantities produced in the thermal and Fe/sub 2/O/sub 3/-catalyzed reactions of 2, both neat and diluted with p-xylene, showed that there were several successive and competing reactions occurring, one of which was independent of the concentration of 2. Further, on the basis of the observation that the product distribution of 3-5, 8, and 10 in the Fe/sub 2/O/sub 3/-catalyzed decomposition of 2 in relatively dilute solution is similar to that observed in the coal reactions, with cyclopropane 8 being the major product in both cases, and that 2 is reacting mainly with the coal, it is concluded that 2 is fairly well dispersed within the coal. In addition, it is clear that swelling of the coal with dioxane did very little to facilitate access of 2 into the coal. Instead the dioxane merely acted to allow for more complete extraction of the products after 2 had reacted with the coal, presumably by keeping the matrix structure more open, than when the dioxane was not used. 26 refs., 2 tabs.

  8. A GIS-based assessment of coal-based hydrogen infrastructure deployment in the state of Ohio

    International Nuclear Information System (INIS)

    Johnson, Nils; Yang, Christopher; Ogden, Joan

    2008-01-01

    Hydrogen infrastructure costs will vary by region as geographic characteristics and feedstocks differ. This paper proposes a method for optimizing regional hydrogen infrastructure deployment by combining detailed spatial data in a geographic information system (GIS) with a technoeconomic model of hydrogen infrastructure components. The method is applied to a case study in Ohio in which coal-based hydrogen infrastructure with carbon capture and storage (CCS) is modeled for two distribution modes at several steady-state hydrogen vehicle market penetration levels. The paper identifies the optimal infrastructure design at each market penetration as well as the costs, CO 2 emissions, and energy use associated with each infrastructure pathway. The results indicate that aggregating infrastructure at the regional-scale yields lower levelized costs of hydrogen than at the city-level at a given market penetration level, and centralized production with pipeline distribution is the favored pathway even at low market penetration. Based upon the hydrogen infrastructure designs evaluated in this paper, coal-based hydrogen production with CCS can significantly reduce transportation-related CO 2 emissions at a relatively low infrastructure cost and levelized fuel cost. (author)

  9. Tungsten deposition by hydrogen-atom reaction with tungsten hexafluoride

    International Nuclear Information System (INIS)

    Lee, W.W.

    1991-01-01

    Using gaseous hydrogen atoms with WF 6 , tungsten atoms can be produced in a gas-phase reaction. The atoms then deposit in a near-room temperature process, which results in the formation of tungsten films. The W atoms (10 10 -10 11 /cm 3 ) were measured in situ by atomic absorption spectroscopy during the CVD process. Deposited W films were characterized by Auger electron spectroscopy, Rutherford backscattering, and X-ray diffraction. The surface morphology of the deposited films and filled holes was studied using scanning electron microscopy. The deposited films were highly adherent to different substrates, such as Si, SiO 2 , Ti/Si, TiN/Si and Teflon. The reaction mechanism and kinetics were studied. The experimental results indicated that this method has three advantages compared to conventional CVD or PECVD: (1) film growth occurs at low temperatures; (2) deposition takes place in a plasma-free environment; and (3) a low level of impurities results in high-quality adherent films

  10. 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

  11. Gasification of coal as efficient means of environment protection and hydrogenation of heavy oils residues

    Energy Technology Data Exchange (ETDEWEB)

    Krichko, A.A.; Maloletnev, A.S. [Fossil Fuel Institute, Moscow (Russian Federation)

    1995-12-31

    The Russia`s more then 50% of coals produced in its European part contain over 2,5% of sulphur, and the coals containing less than 1.5% of sulphurs comprise ca.20%. Thus, utilisation of the sulphide coals is inevitable, and there a problem arises concerning the technology of their sensible use and considering the requirements on the environment protection. Russia`s specialists have developed a design and construction for a steam-gas installation with a closed cycle gasification of the solid fuel. The gasification process will proceed in the fluidized bed under forced pressure of the steam-air blast. Characteristic features of this process are the following: a higher efficiency (the capacity of one gas generator is 3-3,5 times larger than that attained in the present gas generators of the Lurgy`s type): 2-2,5 times decreased fuel losses as compared to the Winkler`s generators; retention of the sensible heat, resulting in an increased total energy efficiency. The main task for petroleum refining industry at the present stage is the increase of depth of oil processing with the aim to intensify motor fuel production. One of the ways to solve the problem is to involve heavy oil residues into the processing. But the high metal and asphaltenes contents in the latter make the application of traditional methods and processes more difficult. Up to now there is no simple and effective technology which could give the opportunity to use oil residues for distillate fractions production. In Fossil fuel institute a process for hydrogenation of high boiling oil products, including with high sulphur, vanadium and nickel contents ones, into distillates and metals concentrates. The main point of the new process is as follows: the water solution of catalytic additive, for which purpose water soluble metal salts of VI-VIII groups are used, is mixed with tar, dispersed and then subjected to additional supercavitation in a special apparatus.

  12. Mechanistic study of the isotopic-exchange reaction between gaseous hydrogen and palladium hydride powder

    International Nuclear Information System (INIS)

    Outka, D.A.; Foltz, G.W.

    1991-01-01

    A detailed mechanism for the isotopic-exchange reaction between gaseous hydrogen and solid palladium hydride is developed which extends previous model for this reaction by specifically including surface reactions. The modeling indicates that there are two surface-related processes that contribute to the overall rate of exchange: the desorption of hydrogen from the surface and the exchange between surface hydrogen and bulk hydrogen. This conclusion is based upon measurements examining the effect of small concentrations of carbon monoxide were helpful in elucidating the mechanism. Carbon monoxide reversibly inhibits certain steps in the exchange; this slows the overall rate of exchange and changes the distribution of products from the reactor

  13. Hydrogen-rich gas production by cogasification of coal and biomass in an intermittent fluidized bed.

    Science.gov (United States)

    Wang, Li-Qun; Chen, Zhao-Sheng

    2013-01-01

    This paper presents the experimental results of cogasification of coal and biomass in an intermittent fluidized bed reactor, aiming to investigate the influences of operation parameters such as gasification temperature (T), steam to biomass mass ratio (SBMR), and biomass to coal mass ratio (BCMR) on hydrogen-rich (H2-rich) gas production. The results show that H2-rich gas free of N2 dilution is produced and the H2 yield is in the range of 18.25~68.13 g/kg. The increases of T, SBMR, and BCMR are all favorable for promoting the H2 production. Higher temperature contributes to higher CO and H2 contents, as well as H2 yield. The BCMR has a weak influence on gas composition, but the yield and content of H2 increase with BCMR, reaching a peak at the BCMR of 4. The H2 content and yield in the product gas increase with SBMR, whilst the content of CO increases first and then decreases correspondingly. At a typical case, the relative linear sensitivity coefficients of H2 production efficiency to T, SBMR, and BCMR were calculated. The results reveal that the order of the influence of the operation parameters on H2 production efficiency is T > SBMR > BCMR.

  14. Novel technique for coal pyrolysis and hydrogenation product analysis. Quarterly report, June 1, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Pfefferle, L.D.

    1992-12-31

    This report covers the last quarter of the last year of the three-year grant period. In the final project year, we concentrated on the pyrolysis and oxidative pyrolysis of large hydrocarbons and mixtures of large and small hydrocarbons in order to develop the VUV-MS technique for compounds more representative of those in coal pyrolysis applications. Special focus was directed at the pyrolysis and oxidative pyrolysis of benzene and benzene acetylene mixtures. The acetylene/benzene mixtures were used to gain a better understanding of the mechanisms of molecular growth in such systems specifically to look at the kinetics of aryl-aryl reactions as opposed to small molecule addition to phenyl radicals. Sarofim and coworkers at MIT have recently demonstrated the importance of these reactions in coal processing environments. In the past, the growth mechanism for the formation of midsized PAH has been postulated to involve primarily successive acetylene additions to phenyl-type radicals, our work confmns this as an important mechanism especially for smaller PAH but also investigates conditions where biaryl formation can play an important role in higher hydrocarbon formation.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hufton, J.; Mayorga, S.; Gaffney, T.; Nataraj, S.; Rao, M.; Sircar, S. [Air Products and Chemicals, Inc., Allentown, PA (United States)

    1998-08-01

    The novel Sorption Enhanced Reaction Process has the potential to decrease the cost of hydrogen production by steam methane reforming. Current effort for development of this technology has focused on adsorbent development, experimental process concept testing, and process development and design. A preferred CO{sub 2} adsorbent, K{sub 2}CO{sub 3} promoted hydrotalcite, satisfies all of the performance targets and it has been scaled up for process testing. A separate class of adsorbents has been identified which could potentially improve the performance of the H{sub 2}-SER process. Although this material exhibits improved CO{sub 2} adsorption capacity compared to the HTC adsorbent, its hydrothermal stability must be improved. Single-step process experiments (not cyclic) indicate that the H{sub 2}-SER reactor performance during the reaction step improves with decreasing pressure and increasing temperature and steam to methane ratio in the feed. Methane conversion in the H{sub 2}-SER reactor is higher than for a conventional catalyst-only reactor operated at similar temperature and pressure. The reactor effluent gas consists of 90+% H{sub 2}, balance CH{sub 4}, with only trace levels (< 50 ppm) of carbon oxides. A best-case process design (2.5 MMSCFD of 99.9+% H{sub 2}) based on the HTC adsorbent properties and a revised SER process cycle has been generated. Economic analysis of this design indicates the process has the potential to reduce the H{sub 2} product cost by 25--31% compared to conventional steam methane reforming.

  16. Mechanism of Wandoan coal liquefaction by the use of tritium and 14C tracer method

    International Nuclear Information System (INIS)

    Kabe, Toshiaki; Nitoh, Osamu; Kawakami, Akira; Marumoto, Motoi; Nakagawa, Kouhei

    1986-01-01

    In order to make the behavior of hydrogen donor solvent clear, Wandoan coal was liquefied in tritium labeled tetralin solvent contained a small amount of 14 C labeled naphthalene, under initial H 2 pressure : 5.9 MPa, reaction temperature range : 400-440 deg C and with or without Ni-Mo-Al 2 O 3 catalyst. The concentration of 14 C in tetralin indicated that the hydrogenation of naphthalene to tetralin occurred. From tritium and hydrogen distributions in coal products, solvents and molecular hydrogen, the amounts of hydrogen which transferred by hydrogen addition and exchange reactions were estimated, and the effects of the catalyst and reaction temperature were examined. Without catalyst, the coal liquefaction proceeded mainly by the hydrogen addition from hydrogen donor solvent to coal and the hydrogen addition from molecular hydrogen to coal products hardly occurred. The catalyst was effective in the hydrocracking of preasphaltenes, but did not promote the hydrocracking of oil. Furthermore, the catalyst promoted the hydrogen addition from molecular hydrogen to coal products and solvents, and activated the hydrogen exchange between molecular hydrogen and solvents, but the hydrogen exchanges did not reach to equilibrium under the condition of 440 deg C. (author)

  17. Co-pyrolysis of waste tire/coal mixtures for smokeless fuel, maltenes and hydrogen-rich gas production

    International Nuclear Information System (INIS)

    Bičáková, Olga; Straka, Pavel

    2016-01-01

    Highlights: • Co-pyrolysis of waste tires/coal mixtures yields mainly smokeless fuel (55–74 wt%). • Alternatively, the smokeless fuel can serve as carbonaceous sorbent. • The obtained tar contained maltenes (80–85 wt%) and asphaltenes (6–8 wt%). • Tar from co-pyrolysis can serve as heating oil or a source of maltenes for repairing of asphalt surfaces. • The hydrogen-rich gas was obtained (61–65 vol% H_2, 24–25 vol% CH_4, 1.4–2 vol% CO_2). - Abstract: The processing of waste tires with two different types of bituminous coal was studied through the slow co-pyrolysis of 1 kg of waste tire/coal mixtures with 15, 30 and 60 wt% waste tires on a laboratory scale. The waste tire/coal mixtures were pyrolysed using a quartz reactor in a stationary bed. The mixtures were heated at a rate 5 °C/min up to the final temperature of 900 °C with a soaking time of 30 min at the required temperature. The mass balance of the process and the properties of the coke and tar obtained were evaluated, further, the influence of the admixture in the charge on the amount and composition of the obtained coke and tar was determined. It was found that the smokeless fuel/carbonaceous sorbent and a high yield of tar for further use can be obtained through the slow co-pyrolysis. The obtained tars contained mostly maltenes (80–85 wt%). FTIR analysis showed that the maltenes from the co-pyrolysis of coal/waste tires exhibited significantly lower aromaticity as compared with that from coal alone. The gas obtained from pyrolysis or co-pyrolysis of waste tire/coal mixtures contained a high amount of hydrogen (above 60 vol%) and methane (above 20 vol%).

  18. Studies of the surface of titanium dioxide. IV. The hydrogen-deuterium equilibration reaction

    International Nuclear Information System (INIS)

    Iwaki, T.; Katsuta, K.; Miura, M.

    1981-01-01

    The interaction of hydrogen with the surface of titanium dioxide has been studied in connection with the hydrogen-reduction mechanism of titanium dioxide, by means of such measurements as weight decrease, magnetic susceptibility, hydrogen uptake, and electrical conductance. It was postulated in the previous study that the rate-determining step of the hydrogen-reduction reaction may be the formation of surface hydroxyl groups, followed by the rapid removal of water molecules from the surface. In this study, the interactions between hydrogen and the surface of titanium dioxide were investigated by measuring the hydrogen-deuterium equilibration reaction, H 2 + D 2 = 2HD, at temperatures above 200 0 C on both surfaces before and after hydrogen reduction to compare the differences in the reactivities

  19. Advances of zeolite based membrane for hydrogen production via water gas shift reaction

    Science.gov (United States)

    Makertihartha, I. G. B. N.; Zunita, M.; Rizki, Z.; Dharmawijaya, P. T.

    2017-07-01

    Hydrogen is considered as a promising energy vector which can be obtained from various renewable sources. However, an efficient hydrogen production technology is still challenging. One technology to produce hydrogen with very high capacity with low cost is through water gas shift (WGS) reaction. Water gas shift reaction is an equilibrium reaction that produces hydrogen from syngas mixture by the introduction of steam. Conventional WGS reaction employs two or more reactors in series with inter-cooling to maximize conversion for a given volume of catalyst. Membrane reactor as new technology can cope several drawbacks of conventional reactor by removing reaction product and the reaction will favour towards product formation. Zeolite has properties namely high temperature, chemical resistant, and low price makes it suitable for membrane reactor applications. Moreover, it has been employed for years as hydrogen selective layer. This review paper is focusing on the development of membrane reactor for efficient water gas shift reaction to produce high purity hydrogen and carbon dioxide. Development of membrane reactor is discussed further related to its modification towards efficient reaction and separation from WGS reaction mixture. Moreover, zeolite framework suitable for WGS membrane reactor will be discussed more deeply.

  20. Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

    International Nuclear Information System (INIS)

    Wiesener, K.; Winkler, E.; Schneider, W.

    1985-01-01

    The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

  1. Novel technique for coal pyrolysis and hydrogenation product analysis. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    Pfefferle, L.D.; Boyle, J.

    1993-03-15

    A microjet reactor coupled to a VUV photoionization time-of-flight mass spectrometer has been used to obtain species measurements during high temperature pyrolysis and oxidation of a wide range of hydrocarbon compounds ranging from allene and acetylene to cyclohexane, benzene and toluene. Initial work focused on calibration of the technique, optimization of ion collection and detection and characterization of limitations. Using the optimized technique with 118 nm photoionization, intermediate species profiles were obtained for analysis of the hydrocarbon pyrolysis and oxidation mechanisms. The ``soft`` ionization, yielding predominantly molecular ions, allowed the study of reaction pathways in these high temperature systems where both sampling and detection challenges are severe. Work has focused on the pyrolysis and oxidative pyrolysis of aliphatic and aromatic hydrocarbon mixtures representative of coal pyrolysis and hydropyrolysis products. The detailed mass spectra obtained during pyrolysis and oxidation of hydrocarbon mixtures is especially important because of the complex nature of the product mixture even at short residence times and low primary reactant conversions. The combustion community has advanced detailed modeling of pyrolysis and oxidation to the C4 hydrocarbon level but in general above that size uncertainties in rate constant and thermodynamic data do not allow us to a priori predict products from mixed hydrocarbon pyrolyses using a detailed chemistry model. For pyrolysis of mixtures of coal-derived liquid fractions with a large range of compound structures and molecular weights in the hundreds of amu the modeling challenge is severe. Lumped models are possible from stable product data.

  2. Study of mobilization and speciation of trace elements in coal pyrolysis

    International Nuclear Information System (INIS)

    Ting, B.T.G.

    1979-01-01

    Various types of coal contain high levels of a number of trace elements. Little is known of the fates of these trace elements during the conversion of coal to liquid and gaseous products. Studies were undertaken of mobilization and speciation of trace elements in coal pyrolysis, one of the major coal conversion processes. The bituminous coal was pyrolyzed to produce liquid and gaseous products. The pyrolysis products were collected in traps in an inert gas stream. In addition mildly hydrogenated coal was prepared by mixing with tetralin, a hydrogen donor solvent, at boiling temperature. In order to characterize each element specifically during pyrolysis, base samples of coal and mildly hydrogenated coal (H-coal) were spiked with heavy metal sulfides, trace metals bound to partially oxidized coal (coal humates), and halide salts prior to carrying out pyrolysis. Eight elements were investigated in this research. They are As, Br, Cl, Co, Cr, Mn, Se, and V. Pre-spiked hydrogenated coal, i.e., pulverized coal spiked with halide salts and heavy metal sulfides then hydrogenated with tetralin, was prepared and studied for the fates of these elements during pyrolysis. Chlorinated and brominated coals were also prepared to compare the volatility differences between organically and inorganically bound halogens during the pyrolysis reaction. These products and the coal char residues were analyzed for the spiked elements mainly by neutron activation analysis for the spiked elements to determine their degree of volatility. Volatility and recovery (mass balance) will be discussed for those elements that appeared highly volatile during pyrolysis. In order to understand the halogenated compounds in the pyrolysis products, gas chromatograms were taken to the collected pyrolysis products of coal, hydrogenated coal, NaCl spiked coal, NaBr spiked coal, chlorinated coal, and brominated coal

  3. Agglomeration and reaction characteristics of various coal chars in fluidized-bed coal gasifier; Ryudoso sekitan gas ka ronai deno sekitan no gyoshu tokusei to hanno tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Uemiya, S.; Aoki, K.; Mori, S.; Kojima, T. [Seikei University, Tokyo (Japan). Faculty of Engineering

    1996-10-28

    With relation to the coals delivered as common samples in the coal fundamental technology development project, an experimental study was conducted on agglomeration characteristics and reaction characteristics in the fluidized-bed coal gasifier. For the experiment, used was a fluidized bed gasifier inserted with a cone-shape dispersion plate with a nozzle in the center. After raising the temperature of the gasifier up to 773K, gasification was conducted sending to the gasifier air from the nozzle and steam from the dispersion plate. The mean particle diameter and gas concentration of chars were measured till the temperature reaches 1373K. As a result of the experiment, it was confirmed that the carbon conversion ratio increases with a decrease in coalification degree of the coal. Moreover, influence of the coal kind was markedly observed at the grid zone of the lower part of the bed, and it was clarified that the lower carbon content ratio the coal kind has, the faster the speed of CO formation and water gasification get. The agglomeration temperature of charcoal which is a product of the condensate is lower by as many as several hundred K than the point of softening, and it was considered to be necessary to study the relation with the temperature distribution in the bed. 3 refs., 3 figs., 1 tab.

  4. Hydrogen production via thermochemical water-splitting by lithium redox reaction

    International Nuclear Information System (INIS)

    Nakamura, Naoya; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

    2013-01-01

    Highlights: •Hydrogen production via water-splitting by lithium redox reactions possibly proceeds below 800 °C. •Entropy control by using nonequilibrium technique successfully reduces the reaction temperature. •The operating temperature should be further reduced by optimizing the nonequilibrium condition to control the cycle. -- Abstracts: Hydrogen production via thermochemical water-splitting by lithium redox reactions was investigated as energy conversion technique. The reaction system consists of three reactions, which are hydrogen generation by the reaction of lithium and lithium hydroxide, metal separation by thermolysis of lithium oxide, and oxygen generation by hydrolysis of lithium peroxide. The hydrogen generation reaction completed at 500 °C. The metal separation reaction is thermodynamically difficult because it requires about 3400 °C in equilibrium condition. However, it was indicated from experimental results that the reaction temperature was drastically reduced to 800 °C by using nonequilibrium technique. The hydrolysis reaction was exothermic reaction, and completed by heating up to 300 °C. Therefore, it was expected that the water-splitting by lithium redox reactions was possibly operated below 800 °C under nonequilibrium condition

  5. Medium temperature reaction between lanthanide and actinide carbides and hydrogen

    International Nuclear Information System (INIS)

    Dean, G.; Lorenzelli, R.; Pascard, R.

    1964-01-01

    Hydrogen is fixed reversibly by the lanthanide and actinide mono carbides in the range 25 - 400 C, as for pure corresponding metals. Hydrogen goes into the carbides lattice through carbon vacancies and the total fixed amount is approximately equal to two hydrogen atoms per initial vacancy. Final products c.n thus be considered as carbo-hydrides of general formula M(C 1-x , H 2x ). The primitive CFC, NaCl type, structure remains unchanged but expands strongly in the case of actinide carbides. With lanthanide carbides, hydrogenation induces a phase transformation with reappearance of the metal structure (HCP). Hydrogen decomposition pressures of all the studied carbo-hydrides are greater than those of the corresponding di-hydrides. (authors) [fr

  6. Achievement report for fiscal 1997 on research under New Sunshine Program. Research on heavy oil hydrogenation and heavy oil/coal coprocessing; 1997 nendo jushitsuyu no suisoka shori narabi ni jushitsuyu/sekitan no coprocessing ni kansuru kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-02-01

    The achievements of the Hokkaido National Industrial Research Institute relating to the titled research are reported. In the study relating to the structural properties of heavy oils, the structures of products of Green River shale oil carbonization is analyzed, heterofunctional groups contained in the oil are subjected to FT-IR (Fourier transform infrared) spectroscopic analysis, and their forms of existence are investigated. In the study relating to the hydrogenation process of heavy oils, findings obtained from experiments are reported, which involve the processing of shale oil by hydrogenation and changes brought about in its chemical structure, hydrogenation of oil sand bitumen, kinetics of hydrocracking of bitumen at a high conversion rate, and a lumping model for bitumen hydrocracking reaction. In the study relating to the coprocessing of heavy oil/coal, coprocessing is experimented for coal and shale oil, coal and oil sand bitumen, and other combinations, and the results are reported. Also, a review is made of the transfer of hydrogen in coprocessing. (NEDO)

  7. Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions.

    Science.gov (United States)

    Arenillas, Ana; Rubiera, Fernando; Pis, José J

    2002-12-15

    Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

  8. Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Kuila, Debasish [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States); Ilias, Shamsuddin [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States)

    2013-02-13

    In steam reforming reactions (SRRs) of alkanes and alcohols to produce H2, noble metals such as platinum (Pt) and palladium (Pd) are extensively used as catalyst. These metals are expensive; so, to reduce noble-metal loading, bi-metallic nanocatalysts containing non-noble metals in MCM-41 (Mobil Composition of Material No. 41, a mesoporous material) as a support material with high-surface area were synthesized using one-pot hydrothermal procedure with a surfactant such as cetyltrimethylammonium bromide (CTAB) as a template. Bi-metallic nanocatalysts of Pd-Ni and Pd-Co with varying metal loadings in MCM-41 were characterized by x-ray diffraction (XRD), N2 adsorption, and Transmission electron microscopy (TEM) techniques. The BET surface area of MCM-41 (~1000 m2/g) containing metal nanoparticles decreases with the increase in metal loading. The FTIR studies confirm strong interaction between Si-O-M (M = Pd, Ni, Co) units and successful inclusion of metal into the mesoporous silica matrix. The catalyst activities were examined in steam reforming of methanol (SRM) reactions to produce hydrogen. Reference tests using catalysts containing individual metals (Pd, Ni and Co) were also performed to investigate the effect of the bimetallic system on the catalytic behavior in the SRM reactions. The bimetallic system remarkably improves the hydrogen selectivity, methanol conversion and stability of the catalyst. The results are consistent with a synergistic behavior for the Pd-Ni-bimetallic system. The performance, durability and thermal stability of the Pd-Ni/MCM-41 and Pd-Co/MCM-41 suggest that these materials may be promising catalysts for hydrogen production from biofuels. A part of this work for synthesis and characterization of Pd-Ni-MCM-41 and its activity for SRM reactions has been published (“Development of Mesoporous Silica Encapsulated Pd-Ni Nanocatalyst for Hydrogen Production” in “Production and Purification of Ultraclean

  9. Co-pyrolysis of waste tire/coal mixtures for smokeless fuel, maltenes and hydrogen-rich gas production

    Czech Academy of Sciences Publication Activity Database

    Bičáková, Olga; Straka, Pavel

    2016-01-01

    Roč. 116, MAY 15 (2016), s. 203-213 ISSN 0196-8904 Grant - others:OPPK(XE) CZ.2.16/3.1.00/21538 Program:OPPK Institutional support: RVO:67985891 Keywords : waste tires * coal * co-pyrolysis * smokeless fuel * tar * hydrogen -rich gas Subject RIV: DM - Solid Waste and Recycling Impact factor: 5.589, year: 2016 http://www.sciencedirect.com/science/article/pii/S0196890416300991

  10. A study on hydrogen bond in coal macerals with in situ diffuse reflectance FTIR by using a new experimental method

    Energy Technology Data Exchange (ETDEWEB)

    Li, D.T.; Li, W.; Sun, Q.L.; Li, B.Q. [Chinese Academy of Science, Taiyuan (China). Inst. for Coal Chemistry

    2003-04-01

    A new method using the small porcelain as the reactor combined with increasing the flow rate of carrier gas was proposed, which has the advantage of excluding the condensation of volatile produced by heated solid samples on the windows during in situ diffuse reflectance FTIR experiment. Moreover, the feasibility of this method was also discussed. Using this method, the distribution and thermal stability of hydrogen bonds in coal macerals obtained from two coals were studied. The results show that the differences between the distribution of hydrogen bonds formed by hydroxyl group in the macerals of two coals were very similar. For the vitrinites the thermal stability of SH-N, carboxylic acid dimmers and self-associated OH is higher than those in inertinites but for OH-N and hydroxyl tetramers and OH-OR{sub 2} there are no obvious laws. For OH-{pi}, its content increased with increasing temperature to 350-380{sup o}C, and then decreased with further heating. The variation of hydrogen bonds in macerals reflects the difference in their structure.

  11. Research of coal flash hydropyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Z.; Zhu, H.; Wu, Y.; Tang, L.; Cheng, L.; Xu, Z. [East China University of Science and Technology, Shanghai (China)

    2001-02-01

    Using x-ray photoelectron spectroscopy (XPS) analyses the organic sufur of seven different Chinese coals and their semi-cokes from flash hydropyrolysis were studied. The results showed that the organic sulfur in coal was alkyal sulfur and thiophene with the peak of XPS located in 163.1-163.5 eV and 164.1-164.5 eV. The relative thiophene content in coal increased with the coal rank. The type of organic sulfur in semi-coke in flash hydropyrolysis was generally thiophene species; its XPS peak also located in 164.1-164.5 eV, and was in accord with its corresponding coal. Total alkyl sulfur and some thiophene sulfur were removed during the flash hydropyrolysis process. The alkyl sulfur had very high activity in hydrogenation reaction. Flash hydropyrolysis was an important new clean-coal technique and had notable desulfurization effect. 13 refs., 2 figs., 4 tabs.

  12. F/Cl + C2H2 reactions: Are the addition and hydrogen abstraction direct processes?

    International Nuclear Information System (INIS)

    Li Jilai; Geng Caiyun; Huang Xuri; Zhan Jinhui; Sun Chiachung

    2006-01-01

    The reactions of atomic radical F and Cl with acetylene have been studied theoretically using ab initio quantum chemistry methods and transition state theory. The doublet potential energy surfaces were calculated at the CCSD(T)/aug-cc-pVDZ//CCSD/6-31G(d,p), CCSD(T)/aug-cc-pVDZ//UMP2/6-311++G(d,p) and compound method Gaussian-3 levels. Two reaction mechanisms including the addition-elimination and the hydrogen abstraction reaction mechanisms are considered. In the addition-elimination reactions, the halogen atoms approach C 2 H 2 , perpendicular to the C≡C triple bond, forming the pre-reactive complex C1 at the reaction entrance. C1 transforms to intermediate isomer I1 via transition state TSC1/1 with a negative/small barrier for C 2 H 2 F/C 2 H 2 Cl system, which can proceed by further eliminating H atom endothermally. While the hydrogen abstraction reactions also involve C1 for the fluorine atom abstraction of hydrogen, yet the hydrogen abstraction by chlorine atom first forms a collinear hydrogen-bonded complex C2. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. According to our results, the presence of pre-reactive complexes indicates that the simple hydrogen abstraction and addition in the halogen atoms reaction with unsaturated hydrocarbon should be more complex. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reactions proceed, we expect that the actual feasibility of the reaction channels may depend on the reaction conditions in the experiment. The present study may be helpful for probing the mechanisms of the title reactions and understanding the halogen chemistry

  13. High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Towards Hydrogen Evolution Reaction

    KAUST Repository

    Coy, Emerson; Yate, Luis; Valencia, Drochss P; Aperador, Willian; Siuzdak, Katarzyna; Torruella, Pau; Azanza, Eduardo; Estrade, Sonia; Iatsunskyi, Igor; Peiró , Francesca; Zhang, Xixiang; Tejada, Javier; Ziolo, Ronald F.

    2017-01-01

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced

  14. Liquid composition having ammonia borane and decomposing to form hydrogen and liquid reaction product

    Science.gov (United States)

    Davis, Benjamin L; Rekken, Brian D

    2014-04-01

    Liquid compositions of ammonia borane and a suitably chosen amine borane material were prepared and subjected to conditions suitable for their thermal decomposition in a closed system that resulted in hydrogen and a liquid reaction product.

  15. Hydrogenation Reactions in Ionic Liquids. The Efficient Reduction of ...

    African Journals Online (AJOL)

    NJD

    2008-12-09

    Dec 9, 2008 ... Volatile organic solvents such as ethanol, methanol and THF are often used for the ... remained consistently high and only declined markedly on the fifth cycle. ... transferral of the viscous liquid from the hydrogenation reactor.

  16. Reactions of oxygen and hydrogen with liquid sodium - a critical survey

    International Nuclear Information System (INIS)

    Ullmann, H.

    1982-01-01

    The fundamentals of solvation chemistry are presented with appropriate components formulated. Methods of investigation and kinetics of the reactions are described. The hydrogen equilibrium pressure and saturation solubilities are described. The chemical equilibrium between O and H in solution is presented with detailed tabulation of the saturation solutions of oxygen, hydrogen and hydroxide in liquid sodium. Agreements and differences with the literature are presented

  17. Coal and biomass-based chemicals via carbonylation, hydroformylation and homologation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sunavala, P.D.; Raghunath, B.

    The paper emphasizes the importance of carbonylation, hydroformylation and homologation reactions in the manufacture of organic chemicals (such as acetic acid, acetic anhydride, cellulose acetate, vinyl acetate monomer, aliphatic amines, isocyanates, methanol, ethanol, n-butanol, ethylene glycol, acrylic acid, etc.) from coal and biomass feedstocks. Topics covered are: synthesis of acetic acid; manufacture of acetic anhydride; synthesis of vinyl acetate monomer by carbonylation; synthesis of aliphatic amines by hydroformylation; synthesis of organic diisocyanates; ethanol synthesis by homologation of methanol; synthesis of ethylene glycol via hydroformylation of formaldehyde; synthesis of n- butanol and n-butyraldehyde by propylene formylation; synthesis of acrylic acid; homologation reaction of carboxylic acid esters with ruthenium catalysts; and synthesis of phenyl isocyanate from nitrobenzene by reductive carbonylation. 26 refs.

  18. Hydrogenation of Phenol over Pt/CNTs: The Effects of Pt Loading and Reaction Solvents

    OpenAIRE

    Feng Li; Bo Cao; Wenxi Zhu; Hua Song; Keliang Wang; Cuiqin Li

    2017-01-01

    Carbon nanotubes (CNTs)-supported Pt nanoparticles were prepared with selective deposition of Pt nanoparticles inside and outside CNTs (Pt–in/CNTs and Pt–out/CNTs). The effects of Pt loading and reaction solvents on phenol hydrogenation were investigated. The Pt nanoparticles in Pt–in/CNTs versus Pt–out/CNTs are smaller and better dispersed. The catalytic activity and reuse stability toward phenol hydrogenation both improved markedly. The dichloromethane–water mixture as the reaction solvent,...

  19. Investigation of the formation of hydrogen cyanide in the coking of kuzbass coal. [Magnitogorsk Integrated Iron and Steel Works-USSR

    Energy Technology Data Exchange (ETDEWEB)

    Grigorev, N.P.; Zhilyaev, Yu.A.; Akulov, P.V.

    1981-01-01

    The experiments were performed using equipment which practically excluded deep pyrolysis of the vapor gas products. The hydrogen cyanide was recovered with 0.1 N caustic soda solution in the temperature range of 500 to 1000/sup 0/C. The HCN concentration was measured photometrically by the acid derivative formed as a result of the reaction of the cyanide radical with the barbituric acid amines. The dynamics of the HCN yield were investigated as a function of the heating rate, the degree of comminuition of the coal types and the charge. 2/3 of the HCN is formed as a result of pyrolysis of the vapor-gas products and 1/3 is attributed to the thermochemical conversion of organic matter.

  20. Fundamental studies on the reaction process of partial hydropyrolysis of coal

    Energy Technology Data Exchange (ETDEWEB)

    O. Yamada; H. Yasuda; M. Kaiho [National Institute of Advanced Industrial Science and Technology, Ibaraki (Japan). Energy Technology Research Institute

    2005-07-01

    In order to make up a simulator to support the development of coal partial hydropyrolysis process, material balance of the reaction was investigated precisely. Amount of H{sub 2} evolved by pyrolysis under inert gas atmosphere was found almost equal to that of (CO+2CO{sub 2}), therefore, most of H{sub 2} seemed to be generated through water gas reaction and shift reaction. CH{sub 4} seemed to be stable even at 1073K and 7.1MPa of H{sub 2}, its generation was simply accelerated in proportion to H{sub 2} pressure. Hydrocarbons, other than CH{sub 4}, were fundamentally unstable at 1073K and 0.93 -7.1MPa of H{sub 2}, however the rate of decomposition of them were so slow that amounts of them evolved were apparently proportion to reaction time and H{sub 2} pressure. BTX and naphthalene were increased apparently with H{sub 2} pressure when the reaction time was less than 5s. 4 refs., 20 figs.

  1. Fe(CO)5-catalyzed coprocessing of coal and heavy oil vacuum residue using syngas-water as a hydrogen source; Fe(CO)5 shokubai ni yoru gosei gas-mizu wo suisogen to suru sekitan-jushitsuyu no coprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Hata, K.; Wada, K.; Mitsudo, T. [Kyoto University, Kyoto (Japan)

    1996-10-28

    Improvement in efficiency and profitability of hydrogenation reaction of heavy hydrocarbon resources is the most important matter to be done. In this study, coprocessing of coal and heavy oil vacuum residue was conducted using syngas-water as a hydrogen source. For the investigation of effect of the reaction temperature during the coprocessing of Wandoan coal and Arabian heavy vacuum residue using Fe(CO)5 as a catalyst, the conversion, 66.0% was obtained at 425{degree}C. For the investigation of effect of reaction time, the yield of light fractions further increased during the two stage reaction at 400{degree}C for 60 minutes and at 425{degree}C for 60 minutes. Finally, almost 100% of THF-soluble matter was obtained through the reaction using 2 mmol of Fe(CO)5 catalyst at 400{degree}C for 60 minutes, and hydrogenation of heavy oil was proceeded simultaneously. When comparing coprocessing reactions using three kinds of hydrogen sources, i.e., hydrogen, CO-water, and syngas-water, the conversion yield and oil yield obtained by using syngas-water were similar to those obtained by using hydrogen, which demonstrated the effectiveness of syngas-water. 2 refs., 2 figs., 2 tabs.

  2. Rate coefficients for hydrogen abstraction reaction of pinonaldehyde

    Indian Academy of Sciences (India)

    The H abstraction reaction from the –CHO group was found to be the most dominant reaction channelamong all the possible reaction pathways and its corresponding rate coefficient at 300 K is kEckart's unsymmetrical= 3.86 ×10-10 cm3 molecule-1 s-1. Whereas the channel with immediate lower activation energy is the ...

  3. Hydrogen storage by reaction between metallic amides and imides

    International Nuclear Information System (INIS)

    Eymery, J.B.; Cahen, S.; Tarascon, J.M.; Janot, R.

    2007-01-01

    This paper details the various metal-N-H systems reported in the literature as possible hydrogen storage materials. In a first part, we discuss the hydrogen storage performances of the Li-N-H system and the desorption mechanism of the LiH-LiNH 2 mixture is especially presented. The possibility of storing hydrogen using two other binary systems (Mg-N-H and Ca-N-H) is described in a second part. In the third part of the paper, we discuss about the performances of the highly promising Li-Mg-N-H system, for which a nice reversibility is obtained at 200 C with an experimental hydrogen capacity of about 5.0 wt.%. Other ternary systems, as Li-B-N-H and Li-Al-N-H, are presented in the last part of this review paper. We especially emphasize the performances obtained in our Laboratory at Amiens with a LiAl(NH 2 ) 4 -LiH mixture able to desorb around 6.0 wt.% of hydrogen at only 130 C. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Jerry Y.S. [Arizona State Univ., Mesa, AZ (United States)

    2013-01-29

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

  5. Nuclear reaction analysis of hydrogen in amorphous silicon and silicon carbide films

    International Nuclear Information System (INIS)

    Guivarc'h, A.; Le Contellec, M.; Richard, J.; Ligeon, E.; Fontenille, J.; Danielou, R.

    1980-01-01

    The 1 H( 11 B, α)αα nuclear reaction is used to determine the H content and the density of amorphous semiconductor Si 1 -sub(x)Csub(x)H 2 and SiHsub(z) thin films. Rutherford backscattering is used to determine the x values and infrared transmission to study the hydrogen bonds. We have observed a transfer or/and a release of hydrogen under bombardment by various ions and we show that this last effect must be taken into account for a correct determination of the hydrogen content. An attempt is made to correlate the hydrogen release with electronic and nuclear energy losses. (orig.)

  6. The Transformation of Coal-Mining Waste Minerals in the Pozzolanic Reactions of Cements

    Directory of Open Access Journals (Sweden)

    Rosario Giménez-García

    2016-06-01

    Full Text Available The cement industry has the potential to become a major consumer of recycled waste materials that are transformed and recycled in various forms as aggregates and pozzolanic materials. These recycled waste materials would otherwise have been dumped in landfill sites, leaving hazardous elements to break down and contaminate the environment. There are several approaches for the reuse of these waste products, especially in relation to clay minerals that can induce pozzolanic reactions of special interest in the cement industry. In the present paper, scientific aspects are discussed in relation to several inert coal-mining wastes and their recycling as alternative sources of future eco-efficient pozzolans, based on activated phyllosilicates. The presence of kaolinite in this waste indicates that thermal treatment at 600 °C for 2 h transformed these minerals into a highly reactive metakaolinite over the first seven days of the pozzolanic reaction. Moreover, high contents of metakaolinite, together with silica and alumina sheet structures, assisted the appearance of layered double hydroxides through metastable phases, forming stratlingite throughout the main phase of the pozzolanic reaction after 28 days (as recommended by the European Standard as the reaction proceeded.

  7. Reaction of hydrogen sulfide with oxygen in the presence of sulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, O.; Tsao, L.

    1983-01-14

    Commonly, abatement of hydrogen sulfide emission from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. We studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDTA are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use. 33 figures, 9 tables.

  8. Reaction of Hydrogen Sulfide with Oxygen in the Presence ofSulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, Oleh; Tsao, Leon

    1983-01-01

    Commonly, abatement of hydrogen sulfide emissions from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One Mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. The authors studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDT are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use.

  9. Diels-Alder reactions in water : Enforced hydrophobic interaction and hydrogen bonding

    NARCIS (Netherlands)

    Engberts, Jan B.F.N.

    1995-01-01

    Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

  10. DIELS-ALDER REACTIONS IN WATER - ENFORCED HYDROPHOBIC INTERACTION AND HYDROGEN-BONDING

    NARCIS (Netherlands)

    Engberts, J.B.F.N.

    Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

  11. An economic study for the co-generation of liquid fuel and hydrogen from coal and municipal solid waste

    International Nuclear Information System (INIS)

    Warren, A.; El-Halwagi, M.

    1996-01-01

    The objective of this paper is to assess the technical and economic feasibility of a new process for co-liquefying coal and plastic wastes. This assessment is based on incorporating recent experimental data on plastic/coal liquefaction within a conceptual process framework. A preliminary design was developed for two process configurations. The primary difference between the configurations is the source of hydrogen (coal versus cellulosic waste). The assessment was based on co-liquefying 720 tons per day of plastic waste with an equivalent amount of coal on a weight basis. The plant products include hydrocarbon gases, naphtha, jet fuel and diesel fuel. Material and energy balances along with plant-wide simulation were conducted for the process. Furthermore, the data on plastic-waste availability, disposal and economics have been compiled. The results from the economic analysis identify profitability criteria for gross profit and thus return on investment based on variable conversion, yield and tipping fee for plastic waste processed. 11 refs., 6 figs

  12. Alkaline hydrothermal de-ashing and desulfurization of low quality coal and its application to hydrogen-rich gas generation

    International Nuclear Information System (INIS)

    Mursito, Anggoro Tri; Hirajima, Tsuyoshi; Sasaki, Keiko

    2011-01-01

    This paper describes experimental research and a fundamental study of alkaline hydrothermal treatment of high-sulfur, high-ash coal from Banten, Java-Indonesia. Experiments were carried out on a laboratory-scale 0.5 L batch reactor. The alkaline hydrothermal treatment gave upgraded clean coal with low sulfur content (about 0.3 wt.%) and low ash content (about 2.1 wt.%). A zero carbon dioxide and pure hydrogen gas were produced at 330 o C by introducing an alkali (sodium hydroxide, NaOH) to the hydrothermal treatment of raw coal. X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques were used to test for the removal or reduction of major inorganic elements in the coal, and changes in carbon-functional groups and their properties were determined by Fourier transform infrared spectroscopy (FTIR) and Carbon-13 of nuclear magnetic resonance ( 13 C NMR) tests on the product of the hydrothermal upgrading and demineralization process.

  13. Distribution of Clay Minerals in Light Coal Fractions and the Thermal Reaction Products of These Clay Minerals during Combustion in a Drop Tube Furnace

    Directory of Open Access Journals (Sweden)

    Sida Tian

    2016-06-01

    Full Text Available To estimate the contribution of clay minerals in light coal fractions to ash deposition in furnaces, we investigated their distribution and thermal reaction products. The light fractions of two Chinese coals were prepared using a 1.5 g·cm−3 ZnCl2 solution as a density separation medium and were burned in a drop-tube furnace (DTF. The mineral matter in each of the light coal fractions was compared to that of the relevant raw coal. The DTF ash from light coal fractions was analysed using hydrochloric acid separation. The acid-soluble aluminium fractions of DTF ash samples were used to determine changes in the amorphous aluminosilicate products with increasing combustion temperature. The results show that the clay mineral contents in the mineral matter of both light coal fractions were higher than those in the respective raw coals. For the coal with a high ash melting point, clay minerals in the light coal fraction thermally transformed more dehydroxylation products compared with those in the raw coal, possibly contributing to solid-state reactions of ash particles. For the coal with a low ash melting point, clay minerals in the light coal fraction produced more easily-slagging material compared with those in the raw coal, playing an important role in the occurrence of slagging. Additionally, ferrous oxide often produces low-melting substances in coal ash. Due to the similarities of zinc oxide and ferrous oxide in silicate reactions, we also investigated the interactions of clay minerals in light coal fractions with zinc oxide introduced by a zinc chloride solution. The extraneous zinc oxide could react, to a small extent, with clay minerals in the coal during DTF combustion.

  14. Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

  15. Rate constant for reaction of atomic hydrogen with germane

    Science.gov (United States)

    Nava, David F.; Payne, Walter A.; Marston, George; Stief, Louis J.

    1990-01-01

    Due to the interest in the chemistry of germane in the atmospheres of Jupiter and Saturn, and because previously reported kinetic reaction rate studies at 298 K gave results differing by a factor of 200, laboratory measurements were performed to determine the reaction rate constant for H + GeH4. Results of the study at 298 K, obtained via the direct technique of flash photolysis-resonance fluorescence, yield the reaction rate constant, k = (4.08 + or - 0.22) x 10(exp -12) cu cm/s.

  16. GaN CVD Reactions: Hydrogen and Ammonia Decomposition and the Desorption of Gallium

    International Nuclear Information System (INIS)

    Bartram, Michael E.; Creighton, J. Randall

    1999-01-01

    Isotopic labeling experiments have revealed correlations between hydrogen reactions, Ga desorption, and ammonia decomposition in GaN CVD. Low energy electron diffraction (LEED) and temperature programmed desorption (TPD) were used to demonstrate that hydrogen atoms are available on the surface for reaction after exposing GaN(0001) to deuterium at elevated temperatures. Hydrogen reactions also lowered the temperature for Ga desorption significantly. Ammonia did not decompose on the surface before hydrogen exposure. However, after hydrogen reactions altered the surface, N 15 H 3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N 2 of mixed isotopes below the onset of GaN sublimation, This suggests that the driving force of the high nitrogen-nitrogen bond strength (226 kcal/mol) can lead to the removal of nitrogen from the substrate when the surface is nitrogen rich. Overall, these findings indicate that hydrogen can influence G-aN CVD significantly, being a common factor in the reactivity of the surface, the desorption of Ga, and the decomposition of ammonia

  17. Overview of light water/hydrogen-based low energy nuclear reactions

    International Nuclear Information System (INIS)

    Miley, George H.; Shrestha, Prajakti J.

    2006-01-01

    This paper reviews light water and hydrogen-based low-energy nuclear reactions (LENRs) including the different methodologies used to study these reactions and the results obtained. Reports of excess heat production, transmutation reactions, and nuclear radiation emission are cited. An aim of this review is to present a summary of the present status of light water LENR research and provide some insight into where this research is heading. (author)

  18. A light water excess heat reaction suggests that cold fusion may be alkali-hydrogen fusion

    International Nuclear Information System (INIS)

    Bush, R.T.

    1992-01-01

    This paper reports that Mills and Kneizys presented data in support of a light water excess heat reaction obtained with an electrolytic cell highly reminiscent of the Fleischmann-Pons cold fusion cell. The claim of Mills and Kneizys that their excess heat reaction can be explained on the basis of a novel chemistry, which supposedly also explains cold fusion, is rejected in favor of their reaction being, instead, a light water cold fusion reaction. It is the first known light water cold fusion reaction to exhibit excess heat, it may serve as a prototype to expand our understanding of cold fusion. From this new reactions are deduced, including those common to past cold fusion studies. This broader pattern of nuclear reactions is typically seen to involve a fusion of the nuclides of the alkali atoms with the simplest of the alkali-type nuclides, namely, protons, deuterons, and tritons. Thus, the term alkali-hydrogen fusion seems appropriate for this new type of reaction with three subclasses: alkali-hydrogen fusion, alkali-deuterium fusion, and alkali-tritium fusion. A new three-dimensional transmission resonance model (TRM) is sketched. Finally, preliminary experimental evidence in support of the hypothesis of a light water nuclear reaction and alkali-hydrogen fusion is reported. Evidence is presented that appears to strongly implicate the transmission resonance phenomenon of the new TRM

  19. Modeling the reaction kinetics of a hydrogen generator onboard a fuel cell -- Electric hybrid motorcycle

    Science.gov (United States)

    Ganesh, Karthik

    Owing to the perceived decline of the fossil fuel reserves in the world and environmental issues like pollution, conventional fuels may be replaced by cleaner alternative fuels. The potential of hydrogen as a fuel in vehicular applications is being explored. Hydrogen as an energy carrier potentially finds applications in internal combustion engines and fuel cells because it is considered a clean fuel and has high specific energy. However, at 6 to 8 per kilogram, not only is hydrogen produced from conventional methods like steam reforming expensive, but also there are storage and handling issues, safety concerns and lack of hydrogen refilling stations across the country. The purpose of this research is to suggest a cheap and viable system that generates hydrogen on demand through a chemical reaction between an aluminum-water slurry and an aqueous sodium hydroxide solution to power a 2 kW fuel cell on a fuel cell hybrid motorcycle. This reaction is essentially an aluminum-water reaction where sodium hydroxide acts as a reaction promoter or catalyst. The Horizon 2000 fuel cell used for this purpose has a maximum hydrogen intake rate of 28 lpm. The study focuses on studying the exothermic reaction between the reactants and proposes a rate law that best describes the rate of generation of hydrogen in connection to the surface area of aluminum available for the certain reaction and the concentration of the sodium hydroxide solution. Further, the proposed rate law is used in the simulation model of the chemical reactor onboard the hybrid motorcycle to determine the hydrogen flow rate to the fuel cell with time. Based on the simulated rate of production of hydrogen from the chemical system, its feasibility of use on different drive cycles is analyzed. The rate of production of hydrogen with a higher concentration of sodium hydroxide and smaller aluminum powder size was found to enable the installation of the chemical reactor on urban cycles with frequent stops and starts

  20. Generalized transition state theory. Quantum effects for collinear reactions of hydrogen molecules and isotopically substituted hydrogen molecules

    International Nuclear Information System (INIS)

    Garrett, B.C.; Truhlar, D.G.

    1979-01-01

    Canonical variational transition state theory, microcanonical variational transition state theory, and Miller's unified statistical theory were used in an attempt to correct two major deficiencies of the conventional transition state theory. These are: (1) the necessity of extra assumptions to include quantum mechanical tunneling effects and (2) the fundamental assumption that trajectories crossing a dividing surface in phase space proceed directly to products. The accuracy of these approximate methods were tested by performing calculations for several collinear reactions of hydrogen, deuterium, chlorine, or iodine, with five isotopes of hydrogen molecules and comparison of these results with those from accurate quantitative calculations of the reaction probabilities as functions of energy and of the thermal rate constants as functions of temperature. 49 references, 28 figures, 17 tables

  1. Reactions of dialkyl hydrogen phosphites with 2,3-diphenylindone

    International Nuclear Information System (INIS)

    Arbuzov, B.A.; Fuzhenkova, A.V.; Banderova, N.A.

    1987-01-01

    Dialkyl hydrogen phosphites are found to add to 2,3-diphenylindone at the carbonyl group with the formation of dialkyl 1-hydroxy-2,3-diphenylinden-1-yl phosphonates, which, under conditions of basic catalysis, are rearranged into diakyl 2,3-diphenylinden-1-yl phosphates, presumably as a result of phosphonate-phosphate rearrangement. Data derived by IR and NMR spectroscopy are included on the electronic and molecular structure of the resulting isomers. Electron density and spin-spin coupling constants are also determined

  2. Process of producing carbonaceous materials; reaction with hydrogen gases

    Energy Technology Data Exchange (ETDEWEB)

    1933-01-13

    A process is described for the production of valuable hydrocarbons by treating distillable carbonaceous materials together with hydrogen gases, under pressure and in contact with catalysts, the process consisting in adding to the original materials, first or during treatment, organic sulfonic acids together with metals from the fourth or eighth groups of the periodic system or a combination of these, or organic carbosilicic acids or inorganic acids containing oxides of sulfur or nitrogen or the anhydrides of these inorganic acids or variation of these compounds.

  3. Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

    Science.gov (United States)

    Dateo, Christopher E.; Walch, Stephen P.

    2002-01-01

    As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

  4. Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels-Alder Reaction.

    Science.gov (United States)

    Kumatabara, Yusuke; Kaneko, Shiho; Nakata, Satoshi; Shirakawa, Seiji; Maruoka, Keiji

    2016-08-05

    A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels-Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a (1) H NMR titration study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Gaseous exchange reaction of deuterium between hydrogen and water on hydrophobic catalyst supporting platinum

    International Nuclear Information System (INIS)

    Izawa, Hirozumi; Isomura, Shohei; Nakane, Ryohei.

    1979-01-01

    The deuterium exchange reaction between hydrogen and water in the gas phase where the fed hydrogen gas is saturated with water vapor is studied experimentally by use of the proper hydrophobic catalysts supporting platinum. It is found that the activities of those catalysts for this reaction system are very high compared with the other known ones for the systems in which gas and liquid should coexist on catalyst surfaces, and that the apparent catalytic activity becomes larger as the amount of platinum supported on a catalyst particle increases. By analyses of the data the following informations are obtained. The exchange reaction can be expressed by a first order reversible reaction kinetics. The pore diffusion in the catalyst particles has significant effect on the overall reaction mechanisms. (author)

  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. Hydrogen isotopic exchange reaction in a trickle-bed

    International Nuclear Information System (INIS)

    Paek, Seung Woo; Ahn, Do Hee; Kim, Kwang Rag; Lee, Min Soo; Yim, Sung Paal; Chung, Hong Suk

    2005-01-01

    The CECE (Combined Electrolysis Catalytic Exchange) with a hydrophobic catalyst is ideally suited for extracting tritium from water because of its high separation factor and mild operating conditions. This process for different hydrogen isotope applications has been developed by AECL. A laboratory scale CECE was built and operated at Mound Laboratory. Belgium and Japan have also developed independently similar processes which are based on a hydrophobic catalyst. The CECE column is composed of an electrolysis cell and a liquid phase catalytic exchange column. The liquid phase catalytic exchange columns having various structures were developed; and it has been recognized that a multistage type and a trickle-bed type are promising. The multistage type gave more successful results than the trickle-bed type. However, the structure of the column is complicated. The trickle-bed type has a significant advantage in that the structure of the column is quite simple: the hydrophobic catalysts or the catalysts and packings are packed within the column. This structure would lead us to a smaller column height than the multistage type. This paper deals with the experiment for the hydrogen isotope exchange in a trickle-bed reactor packed with a hydrophobic catalyst and the design of the catalytic column for the CECE to tritium recovery from light water

  8. Hydrogen isotopic exchange reaction in a trickle-bed

    Energy Technology Data Exchange (ETDEWEB)

    Paek, Seung Woo; Ahn, Do Hee; Kim, Kwang Rag; Lee, Min Soo; Yim, Sung Paal; Chung, Hong Suk [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2005-07-01

    The CECE (Combined Electrolysis Catalytic Exchange) with a hydrophobic catalyst is ideally suited for extracting tritium from water because of its high separation factor and mild operating conditions. This process for different hydrogen isotope applications has been developed by AECL. A laboratory scale CECE was built and operated at Mound Laboratory. Belgium and Japan have also developed independently similar processes which are based on a hydrophobic catalyst. The CECE column is composed of an electrolysis cell and a liquid phase catalytic exchange column. The liquid phase catalytic exchange columns having various structures were developed; and it has been recognized that a multistage type and a trickle-bed type are promising. The multistage type gave more successful results than the trickle-bed type. However, the structure of the column is complicated. The trickle-bed type has a significant advantage in that the structure of the column is quite simple: the hydrophobic catalysts or the catalysts and packings are packed within the column. This structure would lead us to a smaller column height than the multistage type. This paper deals with the experiment for the hydrogen isotope exchange in a trickle-bed reactor packed with a hydrophobic catalyst and the design of the catalytic column for the CECE to tritium recovery from light water.

  9. On line determination of deuterium in hydrogen water exchange reaction by mass spectrometry. IRP-10

    International Nuclear Information System (INIS)

    Sharma, J.D.; Alphonse, K.P.; Mishra, Sushama; Prabhu, S.A.; Mohan, Sadhana; Tangri, V.K.

    2007-01-01

    The Deuterium (D)/Hydrogen (H) analysis at low Concentration is generally carried out by Mass Spectrometry. Mass Spectrometer is specially designed for the measurement of Mass 2 and 3 ratio. The Deuterium analysis of water and hydrogen in concentration range of a few ppm to about 1% plays an important role in the Heavy Water Production Plants. For the enrichment of the Deuterium concentration in H 2 O by H 2 - H 2 O exchange a catalyst is essential as reaction is relatively slow. Heavy Water Division has developed in house Platinum based catalyst for the isotopic exchange of Hydrogen and Water

  10. Cycloaddition Reaction of Hydrogen-Bonded Zn(II)

    Indian Academy of Sciences (India)

    Solid-state Photochemical [2+2] Cycloaddition Reaction of ... and free bpe and lattice water molecules shows face-to-face, π ··· π stacking of two of the four free bpe molecules with coordinated .... were decanted and dried in air. [Yield: 0.068 g ...

  11. Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

    2015-10-05

    Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

  12. The impact of carbon sequestration on the production cost of electricity and hydrogen from coal and natural-gas technologies in Europe in the medium term

    International Nuclear Information System (INIS)

    Tzimas, Evangelos; Peteves, Stathis D.

    2005-01-01

    Carbon sequestration is a distinct technological option with a potential for controlling carbon emissions; it complements other measures, such as improvements in energy efficiency and utilization of renewable energy sources. The deployment of carbon sequestration technologies in electricity generation and hydrogen production will increase the production costs of these energy carriers. Our economic assessment has shown that the introduction of carbon sequestration technologies in Europe in 2020, will result in an increase in the production cost of electricity by coal and natural gas technologies of 30-55% depending on the electricity-generation technology used; gas turbines will remain the most competitive option for generating electricity; and integrated gasification combined cycle technology will become competitive. When carbon sequestration is coupled with natural-gas steam reforming or coal gasification for hydrogen production, the production cost of hydrogen will increase by 14-16%. Furthermore, natural-gas steam reforming with carbon sequestration is far more economically competitive than coal gasification

  13. Reaction dynamics of molecular hydrogen on silicon surfaces

    DEFF Research Database (Denmark)

    Bratu, P.; Brenig, W.; Gross, A.

    1996-01-01

    of the preexponential factor by about one order of magnitude per lateral degree of freedom. Molecular vibrations have practically no effect on the adsorption/desorption dynamics itself, but lead to vibrational heating in desorption with a strong isotope effect. Ab initio calculations for the H-2 interaction...... between the two surfaces. These results indicate that tunneling, molecular vibrations, and the structural details of the surface play only a minor role for the adsorption dynamics. Instead, they appear to be governed by the localized H-Si bonding and Si-Si lattice vibrations. Theoretically, an effective......Experimental and theoretical results on the dynamics of dissociative adsorption and recombinative desorption of hydrogen on silicon are presented. Using optical second-harmonic generation, extremely small sticking probabilities in the range 10(-9)-10(-5) could be measured for H-2 and D-2 on Si(111...

  14. Study of coal flash hydropyrolysis denitrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Lihua; Zhu, Zibin; Zhu, Hongbin; Zhang, Chengfang [Research Institute of Inorganic Chemical Technology, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237 (China)

    2003-05-15

    The hydrodenitrogenation efficiency of 14 types of coals and the reaction mechanism of Zalainouer coal were studied in an experimental entrained bed reactor by flash hydropyrolysis (FHP). The results showed that flash hydropyrolysis is an efficient method for denitrogenation, and that the denitrogenation percentage increases with an increase in temperature and hydrogen pressure. For example, the denitrogenation percentage can reach up to about 60% for Zalainouer coal at 700 C and 6.0 MPa hydrogen pressure. The denitrogenation efficiency of different coal types is related to H/C. According to the conclusion of the study, the denitrogenation percentage increases with the increase in H/C ratio, reaching about 12% when H/C is equal to 0.6, and 40-55% when H/C is above 1.0. The results indicate that FHP is an efficient technique for removing nitrogen in coal.

  15. Certification of the contents (mass fraction) of carbon, hydrogen, nitrogen, chlorine, arsenic, cadmium, manganese, mercury, lead, selenium, vanadium and zinc in three coals. Gas coal CRM No. 180; Coking coal CRM No. 181; Steam coal CRM No. 182

    Energy Technology Data Exchange (ETDEWEB)

    Griepink, B; Colinet, E; Wilkinson, H C

    1986-01-01

    The report first describes the preparation of three coal reference materials: Gas coal (BCR No. 180), Coking coal (BCR No. 181) and Steam coal (BCR No. 182). It deals further with the homogeneity and stability tests for major, minor and trace components. The contents (mass fractions) of the elements: C, H, N, Cl, As, Cd, Mn, Hg, Pb, Se, V and Zn are certified. The analytical techniques used in the certification are summarised. All the individual results are given and recommendations for analysis are made.

  16. Radiation induced chemical reaction of carbon monoxide and hydrogen mixture

    International Nuclear Information System (INIS)

    Sugimoto, Shun-ichi; Nishii, Masanobu

    1985-01-01

    Previous studies of radiation induced chemical reactions of CO-H 2 mixture have revealed that the yields of oxygen containing products were larger than those of hydrocarbons. In the present study, methane was added to CO-H 2 mixture in order to increase further the yields of the oxygen containing products. The yields of most products except a few products such as formaldehyde increased with the addition of small amount of methane. Especially, the yields of trioxane and tetraoxane gave the maximum values when CO-H 2 mixture containing 1 mol% methane was irradiated. When large amounts of methane were added to the mixture, the yields of aldehydes and carboxylic acids having more than two carbon atoms increased, whereas those of trioxane and tetraoxane decreased. From the study at reaction temperature over the range of 200 to 473 K, it was found that the yields of aldehydes and carboxylic acids showed maxima at 323 K. The studies on the effects of addition of cationic scavenger (NH 3 ) and radical scavenger (O 2 ) on the products yields were also carried out on the CO-H 2 -CH 4 mixture. (author)

  17. Reaction of hydroborate anions with liquid hydrogen fluoride

    International Nuclear Information System (INIS)

    Volkov, V.V.; Myakishev, K.G.

    1978-01-01

    The reaction of anhydrous liquid HF with salts of the decahydro-closodecarborate (2) ion B 10 H 10 2- at room temperature or a decreased temperature leads to the formation of complex mixtures of high-molecular boranes with yields of 88 to 92 %. This solid, yellow, nonvolatile product contains traces of B 10 H 14 and B 18 H 22 . The average molecular masses of the borane mixtures obtained are in the range of 438 - 992. The complex composition of the mixtures was confirmed by thin-layer chromatography on silica gel. The IR and NMR spectra of the products are presented. The possible mechanism of the reaction between HF and B 10 H 10 2- with the formation of higher boron hydrides is discussed. Salts of B 12 H 10 2- and B 10 Cl 10 2- do not react with HF; KBF 4 and CsB 9 H 14 are decomposed by HF with the formation of MBF 4

  18. Hydrogen-Oxygen Reaction Assessment in the HANARO Cold Neutron Source

    International Nuclear Information System (INIS)

    Choi, Jung Woon; Kim, Hark Rho; Lee, Kye Hong; Han, Young Soo; Kim, Young Ki; Kim, Seok Hoon; Jeong, Jong Tae

    2006-04-01

    Liquid hydrogen, filled in the moderator cell of the in-pool assembly (IPA), is selected as a moderator to moderate thermal neutrons into cold neutrons for the HANARO Cold Neutron Source. Since the IPA will be installed in the vertical CN hole of the reflector tank at HANARO, the vacuum chamber (VC), the pressure boundary against the reactor, should withstand the detonation pressure so as to avoid any physical damage on the reactor under the hydrogen-oxygen chemical reaction. Accordingly, not only will the vacuum chamber be designed to keep its integrity against the hydrogen accident, but also the hydrogen and vacuum system will be designed with the leak-tight concept and also designed to be surrounded by the inert gas blanket system to prevent any air intrusion into the system. Also, in order to confirm the design concept of the CNS as well as VC integrity against the hydrogen accident, the hydrogen-oxygen chemical reaction is evaluated in this report by several methodologies: AICC methodology, Equivalent TNT detonation methodology, Explosion test result, and Calculation of VC strain under the maximum reflected explosion load

  19. Hydrogen-Oxygen Reaction Assessment in the HANARO Cold Neutron Source

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jung Woon; Kim, Hark Rho; Lee, Kye Hong; Han, Young Soo; Kim, Young Ki; Kim, Seok Hoon; Jeong, Jong Tae

    2006-04-15

    Liquid hydrogen, filled in the moderator cell of the in-pool assembly (IPA), is selected as a moderator to moderate thermal neutrons into cold neutrons for the HANARO Cold Neutron Source. Since the IPA will be installed in the vertical CN hole of the reflector tank at HANARO, the vacuum chamber (VC), the pressure boundary against the reactor, should withstand the detonation pressure so as to avoid any physical damage on the reactor under the hydrogen-oxygen chemical reaction. Accordingly, not only will the vacuum chamber be designed to keep its integrity against the hydrogen accident, but also the hydrogen and vacuum system will be designed with the leak-tight concept and also designed to be surrounded by the inert gas blanket system to prevent any air intrusion into the system. Also, in order to confirm the design concept of the CNS as well as VC integrity against the hydrogen accident, the hydrogen-oxygen chemical reaction is evaluated in this report by several methodologies: AICC methodology, Equivalent TNT detonation methodology, Explosion test result, and Calculation of VC strain under the maximum reflected explosion load.

  20. The reaction of hydrogen atoms with hydrogen peroxide as a function of temperature

    DEFF Research Database (Denmark)

    Lundström, T.; Christensen, H.; Sehested, K.

    2001-01-01

    The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1) and the activa......The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1...

  1. High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei; Wang, Tuo; Jalilov, Almaz S.; Yakobson, Boris I.; Wei, Su-Huai; Tour, James M.

    2017-01-18

    The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.

  2. Shell and explosive hydrogen burning. Nuclear reaction rates for hydrogen burning in RGB, AGB and Novae

    Energy Technology Data Exchange (ETDEWEB)

    Boeltzig, A. [Gran Sasso Science Institute, L' Aquila (Italy); Bruno, C.G.; Davinson, T. [University of Edinburgh, SUPA, School of Physics and Astronomy, Edinburgh (United Kingdom); Cavanna, F.; Ferraro, F. [Dipartimento di Fisica, Universita di Genova (Italy); INFN, Genova (Italy); Cristallo, S. [Osservatorio Astronomico di Collurania, INAF, Teramo (Italy); INFN, Napoli (Italy); Depalo, R. [Dipartimento di Fisica e Astronomia, Universita di Padova, Padova (Italy); INFN, Padova (Italy); DeBoer, R.J.; Wiescher, M. [University of Notre Dame, Institute for Structure and Nuclear Astrophysics, Joint Institute for Nuclear Astrophysics, Notre Dame, Indiana (United States); Di Leva, A.; Imbriani, G. [Dipartimento di Fisica, Universita di Napoli Federico II, Napoli (Italy); INFN, Napoli (Italy); Marigo, P. [Dipartimento di Fisica e Astronomia, Universita di Padova, Padova (Italy); Terrasi, F. [Dipartimento di Matematica e Fisica Seconda Universita di Napoli, Caserta (Italy); INFN, Napoli (Italy)

    2016-04-15

    The nucleosynthesis of light elements, from helium up to silicon, mainly occurs in Red Giant and Asymptotic Giant Branch stars and Novae. The relative abundances of the synthesized nuclides critically depend on the rates of the nuclear processes involved, often through non-trivial reaction chains, combined with complex mixing mechanisms. In this paper, we summarize the contributions made by LUNA experiments in furthering our understanding of nuclear reaction rates necessary for modeling nucleosynthesis in AGB stars and Novae explosions. (orig.)

  3. Exchange reaction of acetylene-d2 with hydrogen chloride

    International Nuclear Information System (INIS)

    Bopp, A.F.; Kern, R.D.

    1975-01-01

    A mixture containing 3 percent each of the reactants C 2 D 2 and HCl in an Ne--Ar diluent was studied over the temperature range 1650 to 2600 0 K utilizing a shock tube coupled to a time-of-flight mass spectrometer. Plots of the mole fractions f of the exchange products, DCl and C 2 HD, revealed two distinct regions of growth: (a) an initial low conversion region characterized by an induction period t/sub i/; and (b) a region of accelerated exchange during which exchange products were formed with a quadratic dependence of the reaction time. These two regions labeled a and b were combined using two empirical equations, 1 - f/sub a//f/sub eq,a/ = exp [-k/sub a/[M]t], where t less than or equal to t/sub i/, and 1 - f/sub b//f/sub eq,b/ = exp [-k/sub b/[M](t - t/sub i/) 2 ], in order to represent the entire reaction profile at any given temperature within the interval investigated. The Arrhenius parameters for k/sub a/ and k/sub b/ were determined to be 10 11 . 15+-0 . 30 exp (-19990 +- 2850/RT) and 10 16 . 40+-0 . 41 exp (-31480 +- 4200/RT), respectively, for DCl and 10 11 . 69+-0 . 29 exp (-19150 +- 2740/RT) and 10 15 . 24+-0 . 34 exp (-17620 +- 3480/RT) for C 2 HD. The units for k/sub a/ are cm 3 mol -1 sec -1 and cm 3 mol -1 sec -2 for k/sub b/. Activation energies are reported in cal mol -1 . Comparison with the profiles obtained for acetylene pyrolysis strongly suggests that the mechanism for the exchange is atomic. Furthermore, the exchange experiments indicate that the initial step in the pyrolysis of acetylene is the disproportionation reaction, 2C 2 H 2 → C 2 H + C 2 H 3

  4. Silicon Nano wires with MoS_x and Pt as Electrocatalysts for Hydrogen Evolution Reaction

    International Nuclear Information System (INIS)

    Hsieh, S.H.; Ho, S.T.; Chen, W.J.

    2016-01-01

    A convenient method was used for synthesizing Pt-nanoparticle//silicon nano wires nano composites. Obtained Pt-/silicon nano wires electrocatalysts were characterized by transmission electron microscopy (TEM). The hydrogen evolution reaction efficiency of the Pt-/silicon nano wire nano composite catalysts was assessed by examining polarization and electrolysis measurements under solar light irradiations. The electrochemical characterizations demonstrate that Pt-/silicon nano wire electrodes exhibited an excellent catalytic activity for hydrogen evolution reaction in an acidic electrolyte. The hydrogen production capability of Pt-/silicon nano wires is also comparable to /silicon nano wires and Pt/silicon nano wires. Electrochemical impedance spectroscopy experiments suggest that the enhanced performance of Pt-/silicon nano wires can be attributed to the fast electron transfer between Pt-/silicon nano wire electrodes and electrolyte interfaces.

  5. Selected specific rates of reactions of transients from water in aqueous solution. II. Hydrogen atom

    International Nuclear Information System (INIS)

    Anbar, M.; Farhataziz; Ross, A.B.

    1975-05-01

    Rates of reactions of hydrogen atoms (from radiolysis of water and other sources) with organic and inorganic molecules, ions, and transients in aqueous solution were tabulated. Directly measured rates obtained by kinetic spectroscopy or conductimetric methods, and relative rates determined by competition kinetics are included. (U.S.)

  6. Symmetrical synergy of hybrid Co9S8-MoSx electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng; Yang, Xiulin; Hedhili, Mohamed N.; Li, Henan; Min, Shixiong; Ming, Jun; Huang, Kuo-Wei; Zhang, Wenjing; Li, Lain-Jong

    2017-01-01

    There exists a strong demand to replace expensive noble metal catalysts with efficient and earth-abundant catalysts for hydrogen evolution reaction (HER). Recently the Co- and Mo-based sulfides such as CoS2, Co9S8, and MoSx have been considered

  7. Determination of the Molar Volume of Hydrogen from the Metal-Acid Reaction: An Experimental Alternative.

    Science.gov (United States)

    de Berg, Kevin; Chapman, Ken

    1996-01-01

    Describes an alternative technique for determining the molar volume of hydrogen from the metal-acid reaction in which the metal sample is encased in a specially prepared cage and a pipette filler is used to fill an inverted burette with water. Eliminates some difficulties encountered with the conventional technique. (JRH)

  8. Numerical comparison of hydrogen-air reaction mechanisms for unsteady shockinduced combustion applications

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, P. Pradeep; Kim, Kui Soon; Oh, Se Jong; Choi, Jeong Yeol [Pusan National University, Busan (Korea, Republic of)

    2015-03-15

    An unsteady shock-induced combustion (SIC) is characterized by the regularly oscillating combustion phenomenon behind the shock wave supported by the blunt projectile flying around the speed of Chapman-Jouguet detonation wave. The SIC is the coupling phenomenon between the hypersonic flow and the chemical kinetics, but the effects of chemical kinetics have been rarely reported. We compared hydrogen-air reaction mechanisms for the shock-induced combustion to demonstrate the importance of considering the reaction mechanisms for such complex flows. Seven hydrogen-air reaction mechanisms were considered, those available publically and used in other researches. As a first step in the comparison of the hydrogen combustion, ignition delay time of hydrogen-oxygen mixtures was compared at various initial conditions. Laminar premixed flame speed was also compared with available experimental data and at high pressure conditions. In addition, half-reaction length of ZND (Zeldovich-Neumann-Doering) detonation structure accounts for the length scale in SIC phenomena. Oscillation frequency of the SIC is compared by running the time-accurate 3rd-order Navier-Stokes CFD code fully coupled with the detailed chemistry by using four levels of grid resolutions.

  9. Numerical comparison of hydrogen-air reaction mechanisms for unsteady shockinduced combustion applications

    International Nuclear Information System (INIS)

    Kumar, P. Pradeep; Kim, Kui Soon; Oh, Se Jong; Choi, Jeong Yeol

    2015-01-01

    An unsteady shock-induced combustion (SIC) is characterized by the regularly oscillating combustion phenomenon behind the shock wave supported by the blunt projectile flying around the speed of Chapman-Jouguet detonation wave. The SIC is the coupling phenomenon between the hypersonic flow and the chemical kinetics, but the effects of chemical kinetics have been rarely reported. We compared hydrogen-air reaction mechanisms for the shock-induced combustion to demonstrate the importance of considering the reaction mechanisms for such complex flows. Seven hydrogen-air reaction mechanisms were considered, those available publically and used in other researches. As a first step in the comparison of the hydrogen combustion, ignition delay time of hydrogen-oxygen mixtures was compared at various initial conditions. Laminar premixed flame speed was also compared with available experimental data and at high pressure conditions. In addition, half-reaction length of ZND (Zeldovich-Neumann-Doering) detonation structure accounts for the length scale in SIC phenomena. Oscillation frequency of the SIC is compared by running the time-accurate 3rd-order Navier-Stokes CFD code fully coupled with the detailed chemistry by using four levels of grid resolutions.

  10. Industrial applications of plasma, microwave and ultrasound techniques : nitrogen-fixation and hydrogenation reactions

    NARCIS (Netherlands)

    Hessel, V.; Cravotto, G.; Fitzpatrick, P.; Patil, B.S.; Lang, J.; Bonrath, W.

    2013-01-01

    The MAPSYN project (Microwave, Acoustic and Plasma assisted SYNtheses) aims at nitrogen-fixation reactions intensified by plasma catalysis and selective hydrogenations intensified by microwaves, possibly assisted by ultrasound. Energy efficiency is the key motif of the project and the call of the

  11. Thermometric titration of cadmium with sodium diethyldithiocarbamate, with oxidation by hydrogen peroxide as indicator reaction.

    Science.gov (United States)

    Hattori, T; Yoshida, H

    1987-08-01

    A new method of end-point indication is described for thermometric titration of cadmium with sodium diethyldithiocarbamate (DDTC). It is based on the redox reaction between hydrogen peroxide added to the system before titration, and the first excess of DDTC. Amounts of cadmium in the range 10-50 mumoles are titrated within 1% error.

  12. Learning about Regiochemistry from a Hydrogen-Atom Abstraction Reaction in Water

    Science.gov (United States)

    Sears-Dundes, Christopher; Huon, Yoeup; Hotz, Richard P.; Pinhas, Allan R.

    2011-01-01

    An experiment has been developed in which the hydrogen-atom abstraction and the coupling of propionitrile, using Fenton's reagent, are investigated. Students learn about the regiochemistry of radical formation, the stereochemistry of product formation, and the interpretation of GC-MS data, in a safe reaction that can be easily completed in one…

  13. Characterisation of hydrocarbonaceous overlayers important in metal-catalysed selective hydrogenation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lennon, David; Warringham, Robbie [School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ (United Kingdom); Guidi, Tatiana [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX (United Kingdom); Parker, Stewart F., E-mail: stewart.parker@stfc.ac.uk [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX (United Kingdom)

    2013-12-12

    Highlights: • Inelastic neutron scattering spectroscopy of a commercial dehydrogenation catalyst. • The overlayer present on the catalyst is predominantly aliphatic. • A population of strongly hydrogen bonded hydroxyls is also present. - Abstract: The hydrogenation of alkynes to alkenes over supported metal catalysts is an important industrial process and it has been shown that hydrocarbonaceous overlayers are important in controlling selectivity profiles of metal-catalysed hydrogenation reactions. As a model system, we have selected propyne hydrogenation over a commercial Pd(5%)/Al{sub 2}O{sub 3} catalyst. Inelastic neutron scattering studies show that the C–H stretching mode ranges from 2850 to 3063 cm{sup −1}, indicating the mostly aliphatic nature of the overlayer and this is supported by the quantification of the carbon and hydrogen on the surface. There is also a population of strongly hydrogen-bonded hydroxyls, their presence would indicate that the overlayer probably contains some oxygen functionality. There is little evidence for any olefinic or aromatic species. This is distinctly different from the hydrogen-poor overlayers that are deposited on Ni/Al{sub 2}O{sub 3} catalysts during methane reforming.

  14. Two-phase model of hydrogen transport to optimize nanoparticle catalyst loading for hydrogen evolution reaction

    DEFF Research Database (Denmark)

    Kemppainen, Erno; Halme, Janne; Hansen, Ole

    2016-01-01

    is the evolution and transport of gaseous H2, since HER leads to the continuous formation of H2 bubbles near the electrode. We present a numerical model that includes the transport of both gaseous and dissolved H2, as well as mass exchange between them, and combine it with a kinetic model of HER at platinum (Pt......) nanoparticle electrodes. We study the effect of the diffusion layer thickness and H2 dissolution rate constant on the importance of gaseous transport, and the effect of equilibrium hydrogen coverage and Pt loading on the kinetic and mass transport overpotentials. Gaseous transport becomes significant when...

  15. A Fluorescent Molecular Probe for the Detection of Hydrogen Based on Oxidative Addition Reactions with Crabtree-Type Hydrogenation Catalysts.

    Science.gov (United States)

    Kos, Pavlo; Plenio, Herbert

    2015-11-02

    A Crabtree-type Ir(I) complex tagged with a fluorescent dye (bodipy) was synthesized. The oxidative addition of H2 converts the weakly fluorescent Ir(I) complex (Φ=0.038) into a highly fluorescent Ir(III) species (Φ=0.51). This fluorogenic reaction can be utilized for the detection of H2 and to probe the oxidative addition step in the catalytic hydrogenation of olefins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

    Directory of Open Access Journals (Sweden)

    Rahul Bhosale

    2016-01-01

    Full Text Available The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2 into Tb and O2, whereas the 2nd step corresponds to the production of H2 through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2 and effect of water splitting temperature (TL on Gibbs free energy related to the H2 production step were examined in detail. The cycle (ηcycle and solar-to-fuel energy conversion (ηsolar-to-fuel efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate that ηcycle and ηsolar-to-fuel increase with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH. It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. At TH=2280 K, by applying 60% heat recuperation, maximum ηcycle of 39.0% and ηsolar-to-fuel of 47.1% for the Tb-WS cycle can be attained.

  17. The effect of moderators on the reactions of hot hydrogen atoms with methane

    CERN Document Server

    Estrup, Peder J.

    1960-01-01

    The reaction of recoil tritium with methane has been examined in further detail. The previous hypothesis that this system involves a hot displacement reaction of high kinetic energy hydrogen to give CH$_{3}$T, CH$_{2}$T and HT is confirmed. The effect of moderator on this process is studied by the addition of noble gases. As predicted these gases inhibit the hot reaction action, their efficiency in this respect being He > Ne > A > Se. The data are quantitatively in accord with a theory of hot atom kinetics. The mechanism of the hot displacement process is briefly discussed.

  18. Ion cyclotron resonance study of reactions of ions with hydrogen atoms

    International Nuclear Information System (INIS)

    Karpas, Z.; Anicich, V.; Huntress, W.T. Jr.

    1979-01-01

    Reactions of H 2 + , HeH + , and CO 2 + ions with hydrogen atoms, and the reactions of D 2 + , CO 2 + , CO + , N 2 + and HCN + with deuterium atoms, were studied using ion cyclotron resonance techniques. These reactions proceed predominantly via a charge transfer mechanism. The rate constants measured are: 6.4, 9.1, 1.1, 5.0, 0.84, 0.90, 1.2, and 0.37 x 10 -10 cm 3 /sec, respectively. Hydrocarbon ions of the types CH/sub n/ + and C 2 H/sub n/ + , where n=2--4, do not react with H or D atoms

  19. Chemical interesterification of soybean oil and fully hydrogenated soybean oil: Influence of the reaction time

    International Nuclear Information System (INIS)

    Ribeiro, Ana Paula Badan; Masuchi, Monise Helen; Grimaldi, Renato; Goncalves, Lireny Aparecida Guaraldo

    2009-01-01

    Chemical interesterification is an important alternative to produce zero trans fats. In practice, however, excessive reaction times are used to ensure complete randomization. This work evaluated the influence of the reaction time on the interesterification of soybean oil/fully hydrogenated soybean oil blend, carried out in the following conditions: 100 deg C, 500 rpm stirring speed, 0.4% (w/w) sodium methoxide catalyst. The triacylglycerol composition, solid fat content and melting point analysis showed that the reaction was very fast, reaching the equilibrium within 5 min. This result suggests the interesterification can be performed in substantially lower times, with reduction in process costs. (author)

  20. Evaluation of a commercial packed bed flow hydrogenator for reaction screening, optimization, and synthesis

    Directory of Open Access Journals (Sweden)

    Marian C. Bryan

    2011-08-01

    Full Text Available The performance of the ThalesNano H-Cube®, a commercial packed bed flow hydrogenator, was evaluated in the context of small scale reaction screening and optimization. A model reaction, the reduction of styrene to ethylbenzene through a 10% Pd/C catalyst bed, was used to examine performance at various pressure settings, over sequential runs, and with commercial catalyst cartridges. In addition, the consistency of the hydrogen flow was indirectly measured by in-line UV spectroscopy. Finally, system contamination due to catalyst leaching, and the resolution of this issue, is described. The impact of these factors on the run-to-run reproducibility of the H-Cube® reactor for screening and reaction optimization is discussed.

  1. Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

    International Nuclear Information System (INIS)

    Santos, Elizabeth; Schmickler, Wolfgang

    2008-01-01

    A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

  2. Incident angle dependence of reactions between graphene and hydrogen atom by molecular dynamics simulation

    International Nuclear Information System (INIS)

    Saito, Seiki; Nakamura, Hiroaki; Ito, Atsushi

    2010-01-01

    Incident angle dependence of reactions between graphene and hydrogen atoms are obtained qualitatively by classical molecular dynamics simulation under the NVE condition with modified Brenner reactive empirical bond order (REBO) potential. Chemical reaction depends on two parameters, i.e., polar angle θ and azimuthal angle φ of the incident hydrogen. From the simulation results, it is found that the reaction rates strongly depend on polar angle θ. Reflection rate becomes larger with increasing θ, and the θ dependence of adsorption rate is also found. The θ dependence is caused by three dimensional structure of the small potential barrier which covers adsorption sites. φ dependence of penetration rate is also found for large θ. (author)

  3. MRI of Heterogeneous Hydrogenation Reactions Using Parahydrogen Polarization

    Energy Technology Data Exchange (ETDEWEB)

    Burt, Scott Russell [Univ. of California, Berkeley, CA (United States)

    2008-01-01

    The power of magnetic resonance imaging (MRI) is its ability to image the internal structure of optically opaque samples and provide detailed maps of a variety of important parameters, such as density, diffusion, velocity and temperature. However, one of the fundamental limitations of this technique is its inherent low sensitivity. For example, the low signal to noise ratio (SNR) is particularly problematic for imaging gases in porous materials due to the low density of the gas and the large volume occluded by the porous material. This is unfortunate, as many industrially relevant chemical reactions take place at gas-surface interfaces in porous media, such as packed catalyst beds. Because of this severe SNR problem, many techniques have been developed to directly increase the signal strength. These techniques work by manipulating the nuclear spin populations to produce polarized} (i.e., non-equilibrium) states with resulting signal strengths that are orders of magnitude larger than those available at thermal equilibrium. This dissertation is concerned with an extension of a polarization technique based on the properties of parahydrogen. Specifically, I report on the novel use of heterogeneous catalysis to produce parahydrogen induced polarization and applications of this new technique to gas phase MRI and the characterization of micro-reactors. First, I provide an overview of nuclear magnetic resonance (NMR) and how parahydrogen is used to improve the SNR of the NMR signal. I then present experimental results demonstrating that it is possible to use heterogeneous catalysis to produce parahydrogen-induced polarization. These results are extended to imaging void spaces using a parahydrogen polarized gas. In the second half of this dissertation, I demonstrate the use of parahydrogen-polarized gas-phase MRI for characterizing catalytic microreactors. Specifically, I show how the improved SNR allows one to map parameters important for characterizing the heat and mass

  4. A kinetic study of reactions of coal with polypropylene and polystyrene

    Czech Academy of Sciences Publication Activity Database

    Straka, Pavel; Náhunková, Jana; Brožová, Zuzana; Zubková, H.

    12(126) (2002), s. 81-84 ISSN 1211-1929 R&D Projects: GA AV ČR IAA2046902 Institutional research plan: CEZ:AV0Z3046908 Keywords : coal * kinetics * polypropylene Subject RIV: DH - Mining, incl. Coal Mining

  5. Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

    International Nuclear Information System (INIS)

    Zamfirescu, C.; Naterer, G.F.; Dincer, I.

    2009-01-01

    The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

  6. Performance assessment of CO2 capture with calcination carbonation reaction process driven by coal and concentrated solar power

    International Nuclear Information System (INIS)

    Zhang, Xuelei; Liu, Yingguang

    2014-01-01

    Calcination carbonation reaction (CCR) process is regarded as a promising option for pulverized coal power plant to mitigate CO 2 emission. In this paper, concentrated solar power (CSP) substitutes for coal to supply part of the calcination energy in order to reduce the fossil fuel consumption associated with the calciner. A CCR process driven by coal and CSP is examined from the perspective of energy efficiency. This paper focuses on the parameters of heat recovery efficiency, CSP capacity, compression energy, air separation energy and recycled energy to determine the contribution of each to the overall energy penalty. In addition, the effects of heat recovery efficiency, CSP capacity, purge percentage and CO 2 capture efficiency on the co-driven case are analyzed through a sensitivity analysis. The results indicate that the thermal efficiency of integrating CCR co-driven process into an ultra-supercritical 1019 MW power plant is 35.37%, which means that the overall efficiency penalty is 9.63 percentage points. Moreover, the co-driven case reduces the fossil fuel consumption and the mass flow rate of fresh sorbent and circulation solids compared with coal-driven case. Increasing heat recovery efficiency and CSP efficiency can improve the co-driven case performance. - Highlights: • We examine a CCR process driven by coal and concentrated solar power simultaneously. • The contributors to the overall energy penalty are quantitatively identified. • Obvious coal-saving effect has been found in the co-driven system. • A sensitivity analysis is conducted to find the impact of key parameters

  7. Decarbonylation and hydrogenation reactions of allyl alcohol and acrolein on Pd(110)

    Science.gov (United States)

    Shekhar, Ratna; Barteau, Mark A.

    1994-11-01

    Allyl alcohol and acrolein reactions on the Pd(110) surface were investigated using temperature programmed desorption. For both unsaturated oxygenates, three coverage-dependent reaction pathways were observed. At low coverages, allyl alcohol decomposed completely to CO, hydrogen and carbonaceous species on the surface. For θ > 0.15 monolayer, ethylene (and small amounts of ethane) desorbed at ca. 295 K. Near saturation coverages, desorption of propanal was detected at ca. 235 K. The parent molecule, allyl alcohol, desorbed only after exposures sufficient to saturate these channels. Acrolein decomposition spectra were similar to those observed for allyl alcohol decomposition on the clean surface. Additional experiments with allyl alcohol on hydrogen- and deuterium-precoveredPd(110) surfaces demonstrated increased hydrogenation of the C 2-hydrocarbon products along with hydrogenation of allyl alcohol to 1-propanol. However, in contrast to previous results for allyl alcohol on the Pd(111) surface, there was no evidence for C-O scission reactions of any C 3 oxygenate on Pd(110).

  8. Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

    1998-01-01

    The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

  9. Molybdenum acetate like precursor of molybdenum carburized supported on alumina: a catalyst for hydrogenation reactions

    International Nuclear Information System (INIS)

    Petkovic, Lucia M; Parra, Ruben D; Marquez Manuel; Larsen, Gustavo

    1994-01-01

    The stability of the Al203 supported dimers under relatively high temperatures and hydrocarbon/H2 (carburizing) atmospheres is reported also, it has been developed a new method for Mo2 loading of the support based on the wet impregnation of the latter. Since carbided Mo is active for hydrogenations, the isobutene/H2 has been chosen as the probe reaction. Al203 supported Mo2(Ac)4 results in a catalyst active for isobutene hydrogenation after treatment with a H2/C2H6 2:1 mixture at 753 k

  10. Regularities of catalytic reactions of hydrogen, ethane and ethylene with elementary sulfur

    International Nuclear Information System (INIS)

    Zazhigalov, V.A.

    1978-01-01

    Shown is the decisive role of metal-sulfur bond stability for activity determination of metal sulfides (WS 2 , MoS 2 , CdS) in interaction reactions of elementary sulfur and hydrogen, ethane and ethylene. Found is the regularity of changing the relative reactiveness of the given substances and a conclusion is made about uniformity of the investigated catalyst processes. The results of hydrogen, ethane and ethylene oxidation by oxygen and sulfur are compared, the semilarity of these processes being pointed out

  11. New method for the hydrogen isotope exchange reaction in a hydrophobic catalyst bed

    International Nuclear Information System (INIS)

    Asakura, Y.; Kikuchi, M.; Yusa, H.

    1982-01-01

    To improve the isotope exchange reaction efficiency between water and hydrogen, a new reactor in which water mists and hydrogen gas react cocurrently was studied. To apply this to the enrichment of tritium in heavy water, a dual temperature isotope exchange reactor which is composed of cocurrent low temperature reactors and the usual countercurrent high temperature reactor was proposed and analyzed using a McCabe-Thiele diagram. By utilizing cocurrent reactors, in combination, the necessary catalyst volume can be reduced to one-tenth as compared with the usual countercurrent low temperature reactor. 17 refs

  12. Study on supported binary sulfide catalysts for secondary hydrogenation of coal-derived liquids; Sekitan ekikayu niji suisoka shokubai no kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, H.; Matsubayashi, N.; Sato, T.; Imamura, M.; Yoshimura, Y.; Nishijima, A. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

    1995-07-28

    To utilize the high performance of supported catalysts in coal liquefaction processes, one of the promising ways is to apply hydroprocessing sulfide catalysts to the secondary hydrogenation of coal-derived liquids which have undergone the solid separation unit. However, when the product yield from the first-stage liquefaction is maximized, the feed stocks in the secondary hydrogenation contain large amounts of residual fractions with preasphaltenes and metallic components. In this case, the development of a long-life catalyst is essential to establish the two-stage process as a practical one. From this viewpoint, the authors have investigated the deactivation causes of supported Ni-Mo sulfide catalysts through the analysis of the used catalysts in the secondary hydrogenation of coal-derived liquids for long periods. The major cause of the catalyst deactivation has been found to be metallic and carbonaceous deposition on the catalyst, which results thin layer which covers the catalyst particles. The catalysts located at the reactor inlet are more rapidly deactivated than those at the rector exit because of larger amounts of metallic foul ants and the above described shell-like layer. Hydrocracking active sites are much heavily deactivated compared with hydrogenation active sites. It is inferred that the basic or polar compounds contained in coal liquids are permanency adsorbed on the hydrocracking active sites. Spectroscopic analysis of the used catalysts clarified the destruction of the active phase of the binary sulfides, through the segregation and crystal growth. The structural changes of the catalysts are very likely caused by heteroatom compounds in the preasphaltenes. Thus, the primary cause of the catalyst deactivation is the preasphaltenes in the coal liquids. Hydroaromatic compounds in the coal liquids suppress the change of the deposited carbonaceous materials into inert coke which permanently deactivate the catalyst.

  13. Hydrogen evolution reaction on electrodes with different PT/C loadings by electrochemical impedance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ortega-Chavez, L. [Inst. Tecnologico de Chihuahua 2, Chihuahua, Chih (Mexico); Ortega-Chavez, L.; Herrera-Peraza, E. [Centro de Investigacion en Materiales Avanzados, Chiuahua, Chih (Mexico); Verde, Y. [Inst. Tecnologico de Cancun, Cancun, Quintana Roo (Mexico)

    2008-04-15

    One of the most widely studied reactions in electrochemistry is the hydrogen evolution reaction (HER). HER is important for the development of water hydrolysis and fuel cell technologies. Because hydrogen-substrate interaction determines oxygen reduction efficiency, an understanding of the chemical and electronic state of hydrogen adsorbed on the electrocatalyst surface is required. Electrochemical impedance spectroscopy (EIS) is a proven highly efficient technique for interface characterization and kinetic parameter determination for different reactions carried out on interfaces. This article presented a study that utilized EIS for characterizing electrodes under HER by implementing a rotating disc electrode with different carbon supported platinum nanoparticles loadings and different potentials in acidic solutions. The results collected by EIS were analyzed in terms of equivalent circuits to calculate different parameters which were compared by statistical analysis. The study also considered the Volmer, Heyrovsky and Tafel steps in the HER reaction as well as a single electro-absorbed intermediate species. The article discussed the experimental set-up with reference to measurements, simulation and fitting. Parameters analysis using ANOVA were reviewed. It was concluded that an increase in impedance occurs when platinum loading decreases in both high and low frequencies. 22 refs., 1 tab., 5 figs.

  14. Numerical simulation of hydrogen-air reacting flows in rectangular channels with catalytic surface reactions

    Science.gov (United States)

    Amano, Ryoichi S.; Abou-Ellail, Mohsen M.; Elhaw, Samer; Saeed Ibrahim, Mohamed

    2013-09-01

    In this work a prediction was numerically modeled for a catalytically stabilized thermal combustion of a lean homogeneous mixture of air and hydrogen. The mixture flows in a narrow rectangular channel lined with a thin coating of platinum catalyst. The solution using an in-house code is based on the steady state partial differential continuity, momentum and energy conservation equations for the mixture and species involved in the reactions. A marching technique is used along the streamwise direction to solve the 2-D plane-symmetric laminar flow of the gas. Two chemical kinetic reaction mechanisms were included; one for the gas phase reactions consisting of 17 elementary reactions; of which 7 are forward-backward reactions while the other mechanism is for the surface reactions—which are the prime mover of the combustion under a lean mixture condition—consisting of 16 elementary reactions. The results were compared with a former congruent experimental work where temperature was measured using thermocouples, while using PLIF laser for measuring water and hydrogen mole fractions. The comparison showed good agreement. More results for the velocities, mole fractions of other species were carried out across the transverse and along the streamwise directions providing a complete picture of overall mechanism—gas and surface—and on the production, consumptions and travel of the different species. The variations of the average OH mole fraction with the streamwise direction showed a sudden increase in the region where the ignition occurred. Also the rate of reactions of the entire surface species were calculated along the streamwise direction and a surface water production flux equation was derived by calculating the law of mass action's constants from the concentrations of hydrogen, oxygen and the rate of formation of water near the surface.

  15. PALLADIUM/COPPER ALLOY COMPOSITE MEMBRANES FOR HIGH TEMPERATURE HYDROGEN SEPARATION FROM COAL-DERIVED GAS STREAMS; F

    International Nuclear Information System (INIS)

    J. Douglas Way; Robert L. McCormick

    2001-01-01

    Recent advances have shown that Pd-Cu composite membranes are not susceptible to the mechanical, embrittlement, and poisoning problems that have prevented widespread industrial use of Pd for high temperature H(sub 2) separation. These membranes consist of a thin ((approx)10(micro)m) film of metal deposited on the inner surface of a porous metal or ceramic tube. Based on preliminary results, thin Pd(sub 60)Cu(sub 40) films are expected to exhibit hydrogen flux up to ten times larger than commercial polymer membranes for H(sub 2) separation, and resist poisoning by H(sub 2)S and other sulfur compounds typical of coal gas. Similar Pd-membranes have been operated at temperatures as high as 750 C. The overall objective of the proposed project is to demonstrate the feasibility of using sequential electroless plating to fabricate Pd(sub 60)Cu(sub 40) alloy membranes on porous supports for H(sub 2) separation. These following advantages of these membranes for processing of coal-derived gas will be demonstrated: High H(sub 2) flux; Sulfur tolerant, even at very high total sulfur levels (1000 ppm); Operation at temperatures well above 500 C; and Resistance to embrittlement and degradation by thermal cycling. The proposed research plan is designed to providing a fundamental understanding of: Factors important in membrane fabrication; Optimization of membrane structure and composition; Effect of temperature, pressure, and gas composition on H(sub 2) flux and membrane selectivity; and How this membrane technology can be integrated in coal gasification-fuel cell systems

  16. Composition, peat-forming vegetation and kerogen paraffinicity of Cenozoic coals: Relationship to variations in the petroleum generation potential (Hydrogen Index)

    Energy Technology Data Exchange (ETDEWEB)

    Petersen, H.I.; Lindstroem, S.; Nytoft, H.P.; Rosenberg, P. [Geological Survey of Denmark and Greenland (GEUS), Oester Voldgade 10, DK-1350 Copenhagen (Denmark)

    2009-04-01

    Coals with similar thermal maturity and from the same deposit normally show a considerable range in petroleum generation potential as measured by the Hydrogen Index (HI). This variation may partly be related to variations in plant input to the precursor mires and organic matter preservation. It is widely accepted that some Cenozoic coals and coaly sediments have the potential to generate oil, which is related to the coal's paraffinicity. Coal paraffinicity is not readily reflected in the bulk HI. In this paper, the relationships between measured HI and coal composition, coal kerogen paraffinicity and floral input have been investigated in detail for three sets of coals from Colombia/Venezuela, Indonesia, and Vietnam. The samples in each coal set are largely of iso-rank. The petroleum generation potential was determined by Rock-Eval pyrolysis. Reflected light microscopy was used to analyse the organic matter (maceral) composition and the thermal maturity was determined by vitrinite reflectance (VR) measurements. The botanical affinity of pollen and spores was analysed by palynology. Coal kerogen paraffinicity was determined by ruthenium tetroxide-catalysed oxidation (RTCO) followed by chain length analysis and quantification (mg/g TOC) of the liberated aliphatic chains. The coals are dominated by huminite, in particular detrohuminite. Only the Vietnamese coals are rich in microscopically visible liptinite. The pollen and spores suggest that the coals were derived principally from complex angiosperm mire vegetations, with subordinate proportions of ferns that generally grew in a subtropical to tropical climate. Measured HI values vary considerably, but for the majority of the coals the values lie between approximately 200 mg HC/g TOC and 300 mg HC/g TOC. Aliphatics yielding monocarboxylic acids dominate in the coal kerogen, whereas aliphatics yielding dicarboxylic acids are secondary. However, the dicarboxylic acids show that cross-linking long-chain aliphatics

  17. Ab initio molecular dynamics simulations for the role of hydrogen in catalytic reactions of furfural on Pd(111)

    Science.gov (United States)

    Xue, Wenhua; Dang, Hongli; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2014-03-01

    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of hydrogen has attracted wide attention. We report ab initio molecular dynamics simulations for furfural and hydrogen on the Pd(111) surface at finite temperatures. The simulations demonstrate that the presence of hydrogen is important in promoting furfural conversion. In particular, hydrogen molecules dissociate rapidly on the Pd(111) surface. As a result of such dissociation, atomic hydrogen participates in the reactions with furfural. The simulations also provide detailed information about the possible reactions of hydrogen with furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

  18. Pd Alloy Membranes for Hydrogen Separation from Coal-Derived Syngas

    National Research Council Canada - National Science Library

    Alptekin, Gokhan O; DeVoss, Sarah; Amalfitano, Bob; Way, Douglas; Thoen, Paul; Lusk, Mark

    2006-01-01

    TDA Research Inc., in collaboration with Colorado School of Mines (CSM) is developing a sulfur and CO-tolerant membrane to produce the clean hydrogen from syngas using Pd membrane films prepared on a variety of supports (e.g...

  19. Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

    Science.gov (United States)

    Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

    2017-02-09

    The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

  20. Japan`s sunshine project. 17.. 1992 annual summary of coal liquefaction and gasification

    Energy Technology Data Exchange (ETDEWEB)

    1993-09-01

    This report describes the achievement of coal liquefaction and gasification technology development in the Sunshine Project for FY 1992. It presents the research and development of coal liquefaction which includes studies on reaction mechanism of coal liquefaction and catalysts for coal liquefaction, the research and development of coal gasification technologies which includes studies on gasification characteristics of various coals and improvement of coal gasification efficiency, the development of bituminous coal liquefaction which includes engineering, construction and operation of a bituminous coal liquefaction pilot plant and research by a process supporting unit (PSU), the development of brown coal liquefaction which includes research on brown coal liquefaction with a pilot plant and development of techniques for upgrading coal oil from brown coal, the development of common base technologies which includes development of slurry letdown valves and study on upgrading technology of coal-derived distillates, the development of coal-based hydrogen production technology with a pilot plant, the development of technology for entrained flow coal gasification, the assessment of coal hydrogasification, and the international co-operation. 4 refs., 125 figs., 39 tabs.

  1. Theoretical study on platinum-catalyzed isotope exchange reaction mechanism of hydrogen and liquid water

    International Nuclear Information System (INIS)

    Hu Sheng; Wang Heyi; Luo Shunzhong

    2009-04-01

    Based on electron and vibration approximate means and the density function theory B3LYP, the ΔG degree and equilibrium pressures of adsorption and dissociation reactions of H 2 and water vapor on Pt surface have been calculated. The adsorption, dissociation and coadsorption actions of H 2 and water were analyzed. According to the ΔG degree, hydrogen molecule combines with metal atoms in single atom, and water vapor molecule has no tendency to dissociate on Pt surface. The dissociation of hydrogen molecule would hold back the direct adsorption of water vapor molecules on Pt surface. The structures of Pt-H (OH 2 ) n + (n=1, 2, 3) hydroniums were optimized. According to the mulliken overlap populations, Pt-H (OH 2 ) + is not stable or produced. Hydrogen isotope exchange occurs between hydration layer and D atoms which adsorb on Pt surface via intermediates (H 2 O) n D + (ads) (n≥2). (authors)

  2. Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

    International Nuclear Information System (INIS)

    Li, Lin; Borry, Richard W.; Iglesia, Enrique

    2000-01-01

    Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

  3. Role of hydrogen bonds in the reaction mechanism of chalcone isomerase.

    Science.gov (United States)

    Jez, Joseph M; Bowman, Marianne E; Noel, Joseph P

    2002-04-23

    In flavonoid, isoflavonoid, and anthocyanin biosynthesis, chalcone isomerase (CHI) catalyzes the intramolecular cyclization of chalcones into (S)-flavanones with a second-order rate constant that approaches the diffusion-controlled limit. The three-dimensional structures of alfalfa CHI complexed with different flavanones indicate that two sets of hydrogen bonds may possess critical roles in catalysis. The first set of interactions includes two conserved amino acids (Thr48 and Tyr106) that mediate a hydrogen bond network with two active site water molecules. The second set of hydrogen bonds occurs between the flavanone 7-hydroxyl group and two active site residues (Asn113 and Thr190). Comparison of the steady-state kinetic parameters of wild-type and mutant CHIs demonstrates that efficient cyclization of various chalcones into their respective flavanones requires both sets of contacts. For example, the T48A, T48S, Y106F, N113A, and T190A mutants exhibit 1550-, 3-, 30-, 7-, and 6-fold reductions in k(cat) and 2-3-fold changes in K(m) with 4,2',4'-trihydroxychalcone as a substrate. Kinetic comparisons of the pH-dependence of the reactions catalyzed by wild-type and mutant enzymes indicate that the active site hydrogen bonds contributed by these four residues do not significantly alter the pK(a) of the intramolecular cyclization reaction. Determinations of solvent kinetic isotope and solvent viscosity effects for wild-type and mutant enzymes reveal a change from a diffusion-controlled reaction to one limited by chemistry in the T48A and Y106F mutants. The X-ray crystal structures of the T48A and Y106F mutants support the assertion that the observed kinetic effects result from the loss of key hydrogen bonds at the CHI active site. Our results are consistent with a reaction mechanism for CHI in which Thr48 polarizes the ketone of the substrate and Tyr106 stabilizes a key catalytic water molecule. Hydrogen bonds contributed by Asn113 and Thr190 provide additional

  4. Experimental determination of reaction rates of water. Hydrogen exchange of tritium with hydrophobic catalysts

    International Nuclear Information System (INIS)

    Bixel, J.C.; Hartzell, B.W.; Park, W.K.

    1976-01-01

    This study was undertaken to obtain data needed for further development of a process for the enrichment and removal of tritium from the water associated with light-water reactors, fuel-reprocessing plants, and tritium-handling laboratories. The approach is based on the use of antiwetting, hydrophobic catalysts which permit the chemical exchange reactions between liquid water and gaseous hydrogen in direct contact, thus eliminating problems of catalyst deactivation and the complexity of reactor design normally associated with current catalytic-detritiation techniques involving gas-phase catalysis. An apparatus and procedure were developed for measuring reaction rates of water-hydrogen chemical exchange with hydrophobic catalysts. Preliminary economic evaluations of the process were made as it might apply to the AGNS fuel reprocessing plant

  5. Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Stoerzinger, Kelsey A. [Physical; Favaro, Marco [Advanced; Joint; Chemical; Ross, Philip N. [Materials; Yano, Junko [Joint; Molecular; Liu, Zhi [State; Division; Hussain, Zahid [Advanced; Crumlin, Ethan J. [Advanced; Joint Center

    2017-11-02

    Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assess the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.

  6. Two-dimensional boron: Lightest catalyst for hydrogen and oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mir, Showkat H. [Centre for Nano Science, Central University of Gujarat, Gandhinagar 382030 (India); Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Jha, Prakash C., E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in [School of Applied Material Sciences, Central University of Gujarat, Gandhinagar 382030 (India); Soni, Himadri [Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen (Germany); Jha, Prafulla K. [Department of Physics, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390 002 (India); Ahuja, Rajeev [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Department of Materials and Engineering, Royal Institute of Technology (KTH), 10044 Stockholm (Sweden)

    2016-08-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) have been envisaged on a two-dimensional (2D) boron sheet through electronic structure calculations based on a density functional theory framework. To date, boron sheets are the lightest 2D material and, therefore, exploring the catalytic activity of such a monolayer system would be quite intuitive both from fundamental and application perspectives. We have functionalized the boron sheet (BS) with different elemental dopants like carbon, nitrogen, phosphorous, sulphur, and lithium and determined the adsorption energy for each case while hydrogen and oxygen are on top of the doping site of the boron sheet. The free energy calculated from the individual adsorption energy for each functionalized BS subsequently guides us to predict which case of functionalization serves better for the HER or the OER.

  7. Influence of sodium dodecyl sulfate on the reaction between Nile Blue A and hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    IVANA A. JANKOVIC

    1999-05-01

    Full Text Available The influence of the anionic surfactant sodium dodecyl sulfate on the rate of the reaction between the cationic form of Nile Blue A and hydrogen peroxide was investigated in the pH range from 5 to 8.5. A retardation of the oxidation of Nile Blue A with hydrogen peroxide of three orders of magnitude was observed at pH 8.5 in the presence of anionic micelles compared to the kinetic data in water. The retardation effect was less pronounced at lower pH values. These effects were explained by the electrostatic interaction of the species involved in the reaction with the negatively charged micellar surface and their effective separation in the vicinity of the micellar surface.

  8. Zinc electrodeposition from flowing alkaline zincate solutions: Role of hydrogen evolution reaction

    Science.gov (United States)

    Dundálek, Jan; Šnajdr, Ivo; Libánský, Ondřej; Vrána, Jiří; Pocedič, Jaromír; Mazúr, Petr; Kosek, Juraj

    2017-12-01

    The hydrogen evolution reaction is known as a parasitic reaction during the zinc electrodeposition from alkaline zincate solutions and is thus responsible for current efficiency losses during the electrolysis. Besides that, the rising hydrogen bubbles may cause an extra convection within a diffusion layer, which leads to an enhanced mass transport of zincate ions to an electrode surface. In this work, the mentioned phenomena were studied experimentally in a flow through electrolyzer and the obtained data were subsequently evaluated by mathematical models. The results prove the indisputable influence of the rising hydrogen bubbles on the additional mixing of the diffusion layer, which partially compensates the drop of the current efficiency of the zinc deposition at higher current flows. Moreover, the results show that the current density ratio (i.e., the ratio of an overall current density to a zinc limiting current density) is not suitable for the description of the zinc deposition, because the hydrogen evolution current density is always involved in the overall current density.

  9. Hydrogen poisoning of the CO oxidation reaction on Pt and Pd under ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Strozier, J.A.

    1977-01-01

    The poisoning by hydrogen of the catalyzed oxidation of CO on Pt and Pd under ultrahigh vacuum conditions was investigated. ac pulsing techniques are used in which the pressure of the reactant CO in the reaction chamber is modulated periodically by means of a fast piezoelectric ultrahigh vacuum valve, and the ac component of the product CO 2 is recorded mass spectroscopically by phase-sensitive techniques. The ac CO 2 production rate is measured as a function of hydrogen pressure (1 - 10 x 10 -9 toor) at constant CO and O 2 pressures (approximately equal to 5 x 10 -8 torr), and constant temperature (approximately equal to 700 K). Exact theoretical calculations of CO 2 production rates were carried out employing several models, i.e., oxygen burn-off by hydrogen, incorporating both the Eley-Rideal and Langmuir-Hinshelwood mechanisms. From a comparison with the experimental results, the probable reaction is of the Langmuir-Hinshelwood type and the relevant rate constant is also determined. These results are compared with other results in the literature on hydrogen oxidation on the surface of Pt

  10. Neutron Scattering in Hydrogenous Moderators, Studied by Time Dependent Reaction Rate Method

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, L G; Moeller, E; Purohit, S N

    1966-03-15

    The moderation and absorption of a neutron burst in water, poisoned with the non-1/v absorbers cadmium and gadolinium, has been followed on the time scale by multigroup calculations, using scattering kernels for the proton gas and the Nelkin model. The time dependent reaction rate curves for each absorber display clear differences for the two models, and the separation between the curves does not depend much on the absorber concentration. An experimental method for the measurement of infinite medium reaction rate curves in a limited geometry has been investigated. This method makes the measurement of the time dependent reaction rate generally useful for thermalization studies in a small geometry of a liquid hydrogenous moderator, provided that the experiment is coupled to programs for the calculation of scattering kernels and time dependent neutron spectra. Good agreement has been found between the reaction rate curve, measured with cadmium in water, and a calculated curve, where the Haywood kernel has been used.

  11. Measure of hydrogen concentration profile in materials by resonant nuclear reactions

    International Nuclear Information System (INIS)

    Livi, R.P.; Zawislak, F.C.; Acquadro, J.C.

    1986-01-01

    The technique for determining the profile of hydrogen concentration in proximities of the surface of materials, is presented. The preliminary measurements were done, using the Pelletron accelerator at Sao Paulo University (USP), in Brazil, for the resonant-nuclear reaction 1 H( 19 F, α γ) 16 O. By using this reaction the technique is sensitive for concentrations above 500 ppm, which could be reduced to 100 ppm through special shieldings and other techniques to reduce the background radiation. (M.C.K.) [pt

  12. 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.

  13. Ruthenium(II) pincer complexes with oxazoline arms for efficient transfer hydrogenation reactions

    KAUST Repository

    Chen, Tao

    2012-08-01

    Well-defined P NN CN pincer ruthenium complexes bearing both strong phosphine and weak oxazoline donors were developed. These easily accessible complexes exhibit significantly better catalytic activity in transfer hydrogenation of ketones compared to their PN 3P analogs. These reactions proceed under mild and base-free conditions via protonation- deprotonation of the \\'NH\\' group in the aromatization-dearomatization process. © 2012 Elsevier Ltd. All rights reserved.

  14. Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

    Energy Technology Data Exchange (ETDEWEB)

    Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H. [KAERI, Taejon (Korea, Republic of)

    2005-11-15

    Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities.

  15. Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

    International Nuclear Information System (INIS)

    Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H.

    2005-01-01

    Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities

  16. Lattice-enabled nuclear reactions in the nickel and hydrogen gas system

    International Nuclear Information System (INIS)

    Nagel, David J.

    2015-01-01

    Thousands of lattice-enabled nuclear reaction (LENR) experiments involving electrochemical loading of deuterium into palladium have been conducted and reported in hundreds of papers. But, it appears that the first commercial LENR power generators will employ gas loading of hydrogen onto nickel. This article reviews the scientific base for LENR in the gas-loaded Ni-H system, and some of the tests of pre-commercial prototype generators based on this combination. (author)

  17. Applications of nuclear reaction analysis for determining hydrogen and deuterium distribution in metals

    International Nuclear Information System (INIS)

    Altstetter, C.J.

    1981-01-01

    The use of ion beams for materials analysis has made a successful transition from the domain of the particle physicist to that of the materials scientist. The subcategory of this field, nuclear reaction analysis, is just now undergoing the transition, particularly in applications to hydrogen in materials. The materials scientist must locate the nearest accelerator, because now he will find that using it can solve mysteries that do not yield to other techniques. 9 figures

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

    Science.gov (United States)

    Alghamdi, Abdulaziz

    2009-12-01

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

  19. Characterization and suitability of superclean coals for hydroliquefaction feedstocks: Final report

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Nam

    1989-05-30

    Superclean coals have been studied for their suitability as liquefaction feedstocks. The effects of ash and sulfur contents and two catalysts on a hydrogen donor solvent liquefaction reaction have been studied. Experiments were run using a unique coal of small particle size (90% <22 microns). The coal was characterized in terms of its chemical and its physical properties. This information made it possible to determine the effects of the static tube flotation separation on the coal. Once characterized the coals were liquefied in the hydrogen donor tetralin under a hydrogen atmosphere of 500 psig. The first series of experiments was to determine the effects of the ash on the liquefaction reaction. The second group of experiments dealt with the effects of catalysts (ammonium molybdate and titanium carbide) on low ash coals at various conditions. A model for batch liquefaction in a hydrogen donor solvent is then developed. This model is based on the assumption that the reaction is due to two competing mechanisms; (1) a thermal decomposition of the coal and (2) a catalytic reaction. The thermal reaction produces unwanted products while the catalytic reaction produces the desired products. To accurately model the batch system, mass transfer is considered. 51 refs., 50 figs., 29 tabs.

  20. Microbial methane from in situ biodegradation of coal and shale: A review and reevaluation of hydrogen and carbon isotope signatures

    Science.gov (United States)

    Vinson, David S.; Blair, Neal E.; Martini, Anna M.; Larter, Steve; Orem, William H.; McIntosh, Jennifer C.

    2017-01-01

    Stable carbon and hydrogen isotope signatures of methane, water, and inorganic carbon are widely utilized in natural gas systems for distinguishing microbial and thermogenic methane and for delineating methanogenic pathways (acetoclastic, hydrogenotrophic, and/or methylotrophic methanogenesis). Recent studies of coal and shale gas systems have characterized in situ microbial communities and provided stable isotope data (δD-CH4, δD-H2O, δ13C-CH4, and δ13C-CO2) from a wider range of environments than available previously. Here we review the principal biogenic methane-yielding pathways in coal beds and shales and the isotope effects imparted on methane, document the uncertainties and inconsistencies in established isotopic fingerprinting techniques, and identify the knowledge gaps in understanding the subsurface processes that govern H and C isotope signatures of biogenic methane. We also compare established isotopic interpretations with recent microbial community characterization techniques, which reveal additional inconsistencies in the interpretation of microbial metabolic pathways in coal beds and shales. Collectively, the re-assessed data show that widely-utilized isotopic fingerprinting techniques neglect important complications in coal beds and shales.Isotopic fingerprinting techniques that combine δ13C-CH4 with δD-CH4 and/or δ13C-CO2have significant limitations: (1) The consistent ~ 160‰ offset between δD-H2O and δD-CH4 could imply that hydrogenotrophic methanogenesis is the dominant metabolic pathway in microbial gas systems. However, hydrogen isotopes can equilibrate between methane precursors and coexisting water, yielding a similar apparent H isotope signal as hydrogenotrophic methanogenesis, regardless of the actual methane formation pathway. (2) Non-methanogenic processes such as sulfate reduction, Fe oxide reduction, inputs of thermogenic methane, anaerobic methane oxidation, and/or formation water interaction can cause the apparent carbon

  1. Sintering uranium oxide in the reaction product of hydrogen-carbon dioxide mixtures

    International Nuclear Information System (INIS)

    De Hollander, W.R.; Nivas, Y.

    1975-01-01

    Compacted pellets of uranium oxide alone or containing one or more additives such as plutonium dioxide, gadolinium oxide, titanium dioxide, silica, and alumina are heated to 900 to 1599 0 C in the presence of a mixture of hydrogen and carbon dioxide, either alone or with an inert carrier gas and held at the desired temperature in this atmosphere to sinter the pellets. The sintered pellets are then cooled in an atmosphere having an oxygen partial pressure of 10 -4 to 10 -18 atm of oxygen such as dry hydrogen, wet hydrogen, dry carbon monoxide, wet carbon monoxide, inert gases such as nitrogen, argon, helium, and neon and mixtures of ayny of the foregoing including a mixture of hydrogen and carbon dioxide. The ratio of hydrogen to carbon dioxide in the gas mixture fed to the furnace is controlled to give a ratio of oxygen to uranium atoms in the sintered particles within the range of 1.98:1 to about 2.10:1. The water vapor present in the reaction products in the furnace atmosphere acts as a hydrolysis agent to aid removal of fluoride should such impurity be present in the uranium oxide. (U.S.)

  2. Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

    Directory of Open Access Journals (Sweden)

    F. Keppler

    2018-05-01

    Full Text Available Chloromethane (CH3Cl is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −264±45 and −280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4 as the target compound with OH and obtained a fractionation constant of −205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

  3. Nitrogen evolution during rapid hydropyrolysis of coal

    Energy Technology Data Exchange (ETDEWEB)

    Xu, W.-C.; Kumagai, M. [Institute of Research and Innovation, Kashiwa (Japan)

    2002-12-01

    The behavior of nitrogen evolution during rapid hydropyrolysis of coal has been investigated at temperatures ranging from 923 to 1123 K and hydrogen pressure up to 5 MPa using a continuous free fall pyrolyzer. Three coals have been tested in this study. The dominant nitrogen gaseous species is ammonia, together with a little amount of HCN because most of HCN is converted to NH{sub 3} through secondary reactions. The results show that the evolution of nitrogen in coal is caused mainly by devolatilization at temperatures below 973 K, while the evolution of volatile nitrogen in char is accelerated with increasing temperature and hydrogen pressure. The mineral matter in coal act as catalysts to promote the evolution of volatile nitrogen in char to N{sub 2} apparently at high temperatures of 1123 K, as found during pyrolysis of coal by Ohtsuka et al. A pseudo-first-order kinetic model was applied to the evolution of nitrogen in coal during rapid hydropyrolysis. The model shows the activation energy for the nitrogen evolution from coal is 36.6 58.6 kJ/mol while the rate of the nitrogen evolution depends on hydrogen pressure in the order of 0.16 0.24. 41 refs., 11 figs., 3 tabs.

  4. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Volume 2, appendices. Final technical report, October 1, 1991--September 30, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., AL (United States); Chander, S. [Pennsylvania State Univ., College Park, PA (United States); Gutterman, C.

    1995-04-01

    Liquefaction experiments were undertaken using subbituminous Black Thunder mine coal to observe the effects of aqueous SO{sub 2} coal beneficiation and the introduction of various coal swelling solvents and catalyst precursors. Aqueous SO{sub 2} beneficiation of Black Thunder coal removed alkali metals and alkaline earth metals, increased the sulfur content and increased the catalytic liquefaction conversion to THF solubles compared to untreated Black Thunder coal. The liquefaction solvent had varying effects on coal conversion, depending upon the type of solvent added. The hydrogen donor solvent, dihydroanthracene, was most effective, while a coal-derived Wilsonville solvent promoted more coal conversion than did relatively inert 1-methylnaphthalene. Swelling of coal with hydrogen bonding solvents tetrahydrofuran (THF), isopropanol, and methanol, prior to reaction resulted in increased noncatalytic conversion of both untreated and SO{sub 2} treated Black Thunder coals, while dimethylsulfoxide (DMSO), which was absorbed more into the coal than any other swelling solvent, was detrimental to coal conversion. Swelling of SO{sub 2} treated coal before liquefaction resulted in the highest coal conversions; however, the untreated coal showed the most improvements in catalytic reactions when swelled in either THF, isopropanol, or methanol prior to liquefaction. The aprotic solvent DMSO was detrimental to coal conversion.

  5. 1H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase

    International Nuclear Information System (INIS)

    Esaki, N.; Nakayama, T.; Sawada, S.; Tanaka, H.; Soda, K.

    1985-01-01

    Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the straight-chain L-amino acids which are not susceptible to elimination. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. For L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically

  6. EPR-spin probe studies of model polymers: separation of covalent cross-linking effects from hydrogen bonding effects in swelled Argonne Premium Coal samples

    Energy Technology Data Exchange (ETDEWEB)

    Spears, D.R.; Sady, W.; Tucker, D.; Kispert, L.D. (University of Alabama, Tuscaloosa, AL (United States). Chemistry Dept.)

    The swelling behaviour of 2-12% cross-linked polystyrene-divinylbenzene (PSDVB) copolymers was examined by an EPR-spin probe technique. It was observed that the mechanism of spin probe inclusion was the intercalation into the matrix rather than diffusion into the pores. The disruption of van der Waals forces between adjacent aromatic rings appeared to be the primary mechanism for pyridine swelling of PSDVB. By comparing the data to results from coal swelling studies it was also inferred that the extent of hydrogen bonding in coal will have a much greater impact on its swelling properties than its covalently cross-linked character. 24 refs., 6 figs.

  7. Development of Mercury and Hydrogen Chloride Emission Monitors for Coal Gasifiers

    Energy Technology Data Exchange (ETDEWEB)

    G. Norton; D. Eckels; C. Chriswell

    2001-02-26

    The gas conditioning issues involved with coal gasification streams are very complex and do not have simple solutions. This is particularly true in view of the fact that the gas conditioning system must deal with tars, high moisture contents, and problems with NH{sub 3} without affecting low ppb levels of Hg, low levels (low ppm or less) of HCl, or the successful operation of conditioner components and analytical systems. Those issues are far from trivial. Trying to develop a non-chemical system for gas conditioning was very ambitious in view of the difficult sampling environment and unique problems associated with coal gasification streams. Although a great deal was learned regarding calibration, sample transport, instrumentation options, gas stream conditioning, and CEM design options, some challenging issues still remain. Sample transport is one area that is often not adequately considered. Because of the gas stream composition and elevated temperatures involved, special attention will need to be given to the choice of materials for the sample line and other plumbing components. When using gas stream oxidation, there will be sample transport regions under oxidizing as well as reducing conditions, and each of those regions will require different materials of construction for sample transport. The catalytic oxidation approach worked well for removal of tars and NH{sub 3} on a short term basis, but durability issues related to using the catalyst tube during extended testing periods still require study.

  8. Effect of hydrogen pressure on free radicals in direct coal liquefaction/coprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Seehra, M.S.; Ibrahim, M.M. [West Virginia Univ., Morgantown, WV (United States)

    1995-12-31

    The objective of this study was to investigate the coprocessing of coal with waste tires and commingled plastics and to characterize the relevant catalysts, using high pressure/high temperature in-situ ESR (Electron Spin Resonance) spectroscopy. The recent results from high pressure ESR spectroscopy are emphasized. During this period, considerable progress was made in developing the high pressure capabilities in in-situ ESR spectroscopy and new results carried out in 1000 psi of H{sub 2}gas are presented. In these experiments, sapphire tubes were used to contain the high pressures at temperatures up to 500{degrees}C. Results of the experiments carried out under 1000 psi of H{sub 2} are compared with those under 1000 psi of non-interacting argon and with the earlier experiments in flowing H{sub 2} gas where the volatiles are removed by the flowing gas. In these experiments, the free radical density N of the Blind Canyon coal was measured at each temperature and pressure by double integration of the ESR signal and calibrating it against a standard. The details of the experimental apparatus and procedures have been described in earlier publications.

  9. Electrocatalysis of the hydrogen evolution reaction by rhenium oxides electrodeposited by pulsed-current

    International Nuclear Information System (INIS)

    Vargas-Uscategui, Alejandro; Mosquera, Edgar; Chornik, Boris; Cifuentes, Luis

    2015-01-01

    Highlights: • Rhenium oxides were produced by means of pulsed current electrodeposition over ITO. • The electrocatalytic behavior of rhenium oxides electrodeposited over ITO was studied. • Electrodeposited rhenium oxides showed electrocatalytic behavior increasing the rate of the hydrogen evolution reaction. • The electrocatalysis behavior was explained considering the relative abundance of Re species on the surface of the electrodeposited material. - Abstract: Rhenium oxides are materials of interest for applications in the catalysis of reactions such as those occurring in fuel cells and photoelectrochemical cells. This research work was devoted to the production of rhenium oxide by means of pulsed current electrodeposition for the electrocatalysis of the hydrogen evolution reaction (HER). Rhenium oxides were electrodeposited over a transparent conductive oxide substrate (Indium Tin-doped Oxide – ITO) in an alkaline aqueous electrolyte. The electrodeposition process allowed the production of rhenium oxides islands (200–600 nm) with the presence of three oxidized rhenium species: Re"I"V associated to ReO_2, Re"V"I associated to ReO_3 and Re"V"I"I associated to H(ReO_4)H_2O. Electrodeposited rhenium oxides showed electrocatalytic behavior over the HER and an increase of one order of magnitude of the exchange current density was observed compared to the reaction taking place on the bare substrate. The electrocatalytic behavior varied with the morphology and relative abundance of oxidized rhenium species in the electrodeposits. Finally, two mechanisms of electrocatalysis were proposed to explain experimental results.

  10. Production of High-Hydrogen Content Coal-Derived Liquids [Part 3 of 3

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Bergin

    2011-03-30

    The primary goal of this project has been to evaluate and compare the effect of the intrinsic differences between cobalt (Co) and iron (Fe) catalysts for Fischer-Tropsch (FT) synthesis using coal-derived syngas. Crude oil, especially heavy, high-sulfur crude, is no longer the appropriate source for the additional, or marginal, amounts of middle-distillate fuels needed to meet growing US and world demand for diesel and jet fuels. Only about 1/3 of the marginal crude oil barrel can be made into diesel and jet fuels. The remaining 2/3 contributes further to global surpluses of by-products. FT can produce these needed marginal, low-sulfur middle-distillate fuels more efficiently, with less environmental impact, and from abundant US domestic resources. Cobalt FT catalyst is more efficient, and less expensive overall, than iron FT catalyst. Mechanisms of cobalt FT catalyst functioning, and poisoning, have been elucidated. Each of these primary findings is amplified by several secondary findings, and these are presented, and verified in detail. The most effective step the United States can take to begin building toward improved long-term national energy security, and to reduce dependence, over time, on imported crude oil from unfriendly and increasingly unstable areas of the world, is to begin producing additional, or marginal amounts of, middle-distillate-type fuels, such as ultralow sulfur diesel (ULSD) and jet fuel (not gasoline) from US domestic resources other than petroleum. FT synthesis of these middle distillate fuels offers the advantage of being able to use abundant and affordable US coal and biomass as the primary feedstocks. Use of the cobalt FT catalyst system has been shown conclusively to be more effective and less expensive than the use of iron FT catalyst with syngas derived from coal, or from coal and biomass combined. This finding is demonstrated in detail for the initial case of a relatively small FT plant of about 2000 barrels per day based upon coal

  11. Production of High-Hydrogen Content Coal-Derived Liquids [Part 2 of 3

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Bergin

    2011-03-30

    The primary goal of this project has been to evaluate and compare the effect of the intrinsic differences between cobalt (Co) and iron (Fe) catalysts for Fischer-Tropsch (FT) synthesis using coal-derived syngas. Crude oil, especially heavy, high-sulfur crude, is no longer the appropriate source for the additional, or marginal, amounts of middle-distillate fuels needed to meet growing US and world demand for diesel and jet fuels. Only about 1/3 of the marginal crude oil barrel can be made into diesel and jet fuels. The remaining 2/3 contributes further to global surpluses of by-products. FT can produce these needed marginal, low-sulfur middle-distillate fuels more efficiently, with less environmental impact, and from abundant US domestic resources. Cobalt FT catalyst is more efficient, and less expensive overall, than iron FT catalyst. Mechanisms of cobalt FT catalyst functioning, and poisoning, have been elucidated. Each of these primary findings is amplified by several secondary findings, and these are presented, and verified in detail. The most effective step the United States can take to begin building toward improved long-term national energy security, and to reduce dependence, over time, on imported crude oil from unfriendly and increasingly unstable areas of the world, is to begin producing additional, or marginal amounts of, middle-distillate-type fuels, such as ultralow sulfur diesel (ULSD) and jet fuel (not gasoline) from US domestic resources other than petroleum. FT synthesis of these middle distillate fuels offers the advantage of being able to use abundant and affordable US coal and biomass as the primary feedstocks. Use of the cobalt FT catalyst system has been shown conclusively to be more effective and less expensive than the use of iron FT catalyst with syngas derived from coal, or from coal and biomass combined. This finding is demonstrated in detail for the initial case of a relatively small FT plant of about 2000 barrels per day based upon coal

  12. Production of High-Hydrogen Content Coal-Derived Liquids [Part 1 of 3

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Bergin

    2011-03-30

    The primary goal of this project has been to evaluate and compare the effect of the intrinsic differences between cobalt (Co) and iron (Fe) catalysts for Fischer-Tropsch (FT) synthesis using coal-derived syngas. Crude oil, especially heavy, high-sulfur crude, is no longer the appropriate source for the additional, or marginal, amounts of middle-distillate fuels needed to meet growing US and world demand for diesel and jet fuels. Only about 1/3 of the marginal crude oil barrel can be made into diesel and jet fuels. The remaining 2/3 contributes further to global surpluses of by-products. FT can produce these needed marginal, low-sulfur middle-distillate fuels more efficiently, with less environmental impact, and from abundant US domestic resources. Cobalt FT catalyst is more efficient, and less expensive overall, than iron FT catalyst. Mechanisms of cobalt FT catalyst functioning, and poisoning, have been elucidated. Each of these primary findings is amplified by several secondary findings, and these are presented, and verified in detail. The most effective step the United States can take to begin building toward improved long-term national energy security, and to reduce dependence, over time, on imported crude oil from unfriendly and increasingly unstable areas of the world, is to begin producing additional, or marginal amounts of, middle-distillate-type fuels, such as ultralow sulfur diesel (ULSD) and jet fuel (not gasoline) from US domestic resources other than petroleum. FT synthesis of these middle distillate fuels offers the advantage of being able to use abundant and affordable US coal and biomass as the primary feedstocks. Use of the cobalt FT catalyst system has been shown conclusively to be more effective and less expensive than the use of iron FT catalyst with syngas derived from coal, or from coal and biomass combined. This finding is demonstrated in detail for the initial case of a relatively small FT plant of about 2000 barrels per day based upon coal

  13. Purification of hydrogen under a free or combined form in a gaseous mixture, by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Caron Charles, M.

    1988-03-01

    Within the framework of the european fusion program, we are dealing with the purification of hydrogen (tritium) under a free or combined form, from a H 2 , N 2 , NH 3 , CH 4 , O 2 , gaseous mixture. The process consists in cracking the hydrogenated molecules and absorbing the impurities by chemical reactions with uranium, without holding back hydrogen. In the temperature range: 950 K [fr

  14. Exchange reaction between hydrogen and deuterium. II - Proposal for an heterogeneous initiation mechanism of gaseous phase reactions

    Energy Technology Data Exchange (ETDEWEB)

    Marteau, Chantal; Gaillard-Cusin, Francoise; James, Henri [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

    1978-05-01

    Investigation of experimental data related to evolution period exhibited by H/sub 2/-D/sub 2/ exchange process requires to take into account the variation against time of every atomic species -adsorbed or not- implied in the reaction mechanism. The formation of first chain carriers involves: - chemisorption of either gaseous reactant on the surface active centres (..sigma..), e.g.: ..sigma.. + 1/2 H/sub 2/ reversible ..sigma..H; - consecutive generation of atomic species through hetero-homogeneous transfer between chemisorbed species (..sigma..H) and gaseous molecules: ..sigma..H+H/sub 2/..--> sigma..+H/sub 2/+H/sup 0/, ..sigma..H+D/sub 2/..--> sigma..+HD+D/sup 0/. Therefore, it can be shown that the heterogeneous initiation process of a gas phase reaction identifies to a chain linear mechanism. Such an heterogeneous sequence conditions the further proceeding of the homogeneous chain reaction; both evolutions being kinematically connected. Rate constant of hydrogen adsorption on silica glass: ksub(a1) approximately 10/sup 14/ exp(-47/RT)Isup(0,5).molesup(-0,5).S/sup -1/ has been evaluated.

  15. A contribution to the study of the hydrogen evolution reaction on tungsten under water electrolysis conditions

    International Nuclear Information System (INIS)

    Tanaka, A.A.; Avaca, L.A.; Gonzalez, E.R.

    1984-01-01

    Tungsten, electrodeposited on mild steel from aqueous solutions, has been shown to behave similarly to electroplated nickel when used as a cathode in 28% KOH at 60 0 C and current densities of the order of 135 mA cm -2 . When compared with bare mild steel the tungsten cathodes present an overpotential 50mV higher, but this is largely compensated by the extremely higher chemical stability of the deposits in the electrolyte. This is particularly important when the electrolyzer is going to be used in an intermittent fashion. In the present work, the hydrogen evolution reaction was studied on pure and electrodeposited tungsten electrodes in alkaline solutions through the recording of steady-state polarization curves. By comparison of the experimental electrochemical parameters with those predicted by theory, it was established that the mechanism of the reaction is of the type Volmer-Heyrowsky, with the electrochemical desorption reaction being the rate determining step

  16. Rational design of competitive electrocatalysts for the oxygen reduction reaction in hydrogen fuel cells

    Science.gov (United States)

    Stolbov, Sergey; Alcántara Ortigoza, Marisol

    2012-02-01

    The large-scale application of one of the most promising clean and renewable sources of energy, hydrogen fuel cells, still awaits efficient and cost-effective electrocatalysts for the oxygen reduction reaction (ORR) occurring on the cathode. We demonstrate that truly rational design renders electrocatalysts possessing both qualities. By unifying the knowledge on surface morphology, composition, electronic structure and reactivity, we solve that sandwich-like structures are an excellent choice for optimization. Their constituting species couple synergistically yielding reaction-environment stability, cost-effectiveness and tunable reactivity. This cooperative-action concept enabled us to predict two advantageous ORR electrocatalysts. Density functional theory calculations of the reaction free-energy diagrams confirm that these materials are more active toward ORR than the so far best Pt-based catalysts. Our designing concept advances also a general approach for engineering materials in heterogeneous catalysis.

  17. The solvation reaction field for a hydrogen atom in a dielectric continuum

    International Nuclear Information System (INIS)

    Chipman, D.M.

    1996-01-01

    A reaction field exists even for a nonpolar solute embedded in a spherical cavity within a surrounding homogeneous dielectric continuum. This arises from the tail of the electronic wave function that penetrates beyond the cavity boundary into the dielectric region. This effect, which is neglected or treated only in cursory fashion in most reaction field implementations, is examined in detail for the simple case of a ground state hydrogen atom, where very accurate solutions of the relevant equations can be obtained. Properties considered include the penetration of the electron outside the cavity, the electronic density at the nucleus, the electron binding energy, the electrostatic free energy of solvation, the polarizability, and the vertical 1s→2p excitation energy. Also, the effect of the common approximation of neglecting the volume polarization and treating only the surface polarization contribution to the reaction field is critically evaluated. copyright 1996 American Institute of Physics

  18. MoS2 @HKUST-1 Flower-Like Nanohybrids for Efficient Hydrogen Evolution Reactions.

    Science.gov (United States)

    Wang, Chengli; Su, Yingchun; Zhao, Xiaole; Tong, Shanshan; Han, Xiaojun

    2018-01-24

    A novel MoS 2 -based flower-like nanohybrid for hydrogen evolution was fabricated through coating the Cu-containing metal-organic framework (HKUST-1) onto MoS 2 nanosheets. It is the first time that MoS 2 @HKUST-1 nanohybrids have been reported for the enhanced electrochemical performance of HER. The morphologies and components of the MoS 2 @HKUST-1 flower-like nanohybrids were characterized by scanning electron microscopy, X-ray diffraction analysis and Fourier transform infrared spectroscopy. Compared with pure MoS 2 , the MoS 2 @HKUST-1 hybrids exhibit enhanced performance on hydrogen evolution reaction with an onset potential of -99 mV, a smaller Tafel slope of 69 mV dec -1 , and a Faradaic efficiency of nearly 100 %. The MoS 2 @HKUST-1 flower-like nanohybrids exhibit excellent stability in acidic media. This design opens new possibilities to effectively synthesize non-noble metal catalysts with high performance for the hydrogen evolution reaction (HER). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Production of hydrogen through the carbonation-calcination reaction applied to CH4/CO2 mixtures

    International Nuclear Information System (INIS)

    Barelli, L.; Bidini, G.; Corradetti, A.; Desideri, U.

    2007-01-01

    The production of hydrogen combined with carbon capture represents a possible option for reducing CO 2 emissions in atmosphere and anthropogenic greenhouse effect. Nowadays the worldwide hydrogen production is based mainly on natural gas reforming, but the attention of the scientific community is focused also on other gas mixtures with significant methane content. In particular mixtures constituted mainly by methane and carbon dioxide are extensively used in energy conversion applications, as they include land-fill gas, digester gas and natural gas. The present paper addresses the development of an innovative system for hydrogen production and CO 2 capture starting from these mixtures. The plant is based on steam methane reforming, coupled with the carbonation and calcination reactions for CO 2 absorption and desorption, respectively. A thermodynamic approach is proposed to investigate the plant performance in relation to the CH 4 content in the feeding gas. The results suggest that, in order to optimize the hydrogen purity and the efficiency, two different methodologies can be adopted involving both the system layout and operating parameters. In particular such methodologies are suitable for a methane content, respectively, higher and lower than 65%

  20. Method for increasing the calorific value of gas produced by the in situ combustion of coal

    Science.gov (United States)

    Shuck, Lowell Z.

    1978-01-01

    The present invention relates to the production of relatively high Btu gas by the in situ combustion of subterranean coal. The coal bed is penetrated with a horizontally-extending borehole and combustion is initiated in the coal bed contiguous to the borehole. The absolute pressure within the resulting combustion zone is then regulated at a desired value near the pore pressure within the coal bed so that selected quantities of water naturally present in the coal will flow into the combustion zone to effect a hydrogen and carbon monoxide-producing steam-carbon reaction with the hot carbon in the combustion zone for increasing the calorific value of the product gas.

  1. Study on Al2O3 extraction from activated coal gangue under different calcination atmospheres

    Science.gov (United States)

    Dong, Ling; Liang, Xinxing; Song, Qiang; Gao, Gewu; Song, Lihua; Shu, Yuanfeng; Shu, Xinqian

    2017-12-01

    Coal gangue was calcinated under air, nitrogen, carbon dioxide, air-hydrogen, and hydrogen atmospheres. The effects of different calcination temperatures and atmospheres on the mineral composition of activated coal gangue were investigated by X-ray diffraction. Moreover, the acid leaching kinetics of aluminum oxide from coal gangue was investigated with sulfuric acid. It showed that the air atmosphere promoted kaolinite decomposition during coal gangue calcination. The hydrogen atmosphere promoted the activation and decomposition of kaolinite at reaction temperatures exceeding 650°C. The carbon dioxide atmosphere eliminated the influence of residual carbon on coal gangue. When the ratio of acid/coal gangue was 1.5 and reaction temperature was 650°C, the sulfuric acid leaching rate under air, air-hydrogen, carbon dioxide, hydrogen and nitrogen atmospheres were 93.66%, 90.90%, 84.06%, 81.91% and 77.54% respectively. The acid leaching reaction process conformed to unreacted shrinking core model of particle unchanged, and was controlled by the interfacial chemical reaction. The reaction kinetic equation for the leaching process was 1-(1-x)1/3=kt with an apparent activation energy of 48.97 kJ/mol.

  2. Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

    KAUST Repository

    Dehury, Niranjan

    2016-07-18

    Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

  3. Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

    Science.gov (United States)

    Athokpam, Bijyalaxmi; Ramesh, Sai G.

    2018-04-01

    We present a study of the abstraction of alkyl hydrogen atoms from the β and α positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 × 2 EVB models for the Hβ and Hα reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the Hα abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode.

  4. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction. Final technical report, September 1, 1988--December 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Eisch, J.J.

    1992-04-07

    The ultimate objective of this research has been to uncover novel reagents and experimental conditions for heteroatom removal and hydrogen transfer processes, which would be applicable to the liquefaction of coal under low-severity conditions. To this end, one phase of this research has investigated the cleavage of carbon-heteroatom bonds involving sulfur, oxygen, nitrogen and halogen by subvalent transition-metal complexes. A second phase of the study has assessed the capability of the same transition-metal complexes or of organoaluminum Lewis acids to catalyze the cleavage of carbon-hydrogen bonds in aromatics and hence to promote hydrogen shuttling. Finally, a third phase of our work has uncovered a remarkable synergistic effect of combinations of transition metals with organoaluminum Lewis acids on hydrogen shuttling between aromatics and hydroaromatics. (VC)

  5. Flash hydropyrolysis of coal using a small scale of free fall reactor

    Energy Technology Data Exchange (ETDEWEB)

    Miura, K.; Morozumi, F. [Kyoto University, Kyoto (Japan). Department of Chemical Engineering

    1998-07-01

    A small scale of high-pressure free fall reactor was developed for the flash hydropyrolysis of coal. Taiheiyo coal (a Japanese subbituminous coal) was pyrolysed under a high hydrogen pressure without difficulty by use of this reactor. The effect of gas atmosphere, residence time, pressure, and temperature on the product yield was examined in detail. A flash hydropyrolysis reaction model was developed based on the experimental data, and its validity was examined. 8 refs., 5 figs., 1 tab.

  6. CALCULATION OF REACTION COMPLETENESS AND SUBSTANCE TRANSFORMATION AT WATER-COAL GASIFICATION

    Directory of Open Access Journals (Sweden)

    N. S. Nazarov

    2007-01-01

    Full Text Available Process of water-coal gasification is satisfactorily described by three thermal and chemical equations; using these equations composition of gasification product (water carbon monoxide gas has been calculated in accordance with a temperature. Results of the calculations are presented in the form of charts. 

  7. Ultravitrinite coals from Chukotka

    Energy Technology Data Exchange (ETDEWEB)

    Lapo, A.V.; Letushova, I.A.

    1979-03-01

    Chemical and petrographic analysis was conducted on coals from the Anadyrya and Bukhti Ugol'noi deposits. Characteristics of the most prevalent type of vitrinite coals in both regions are presented here. Anadyrya coals belong to a transitional phase between brown coal and long flame. Ultravitrinite coals predominate. Gas coals from Bukti Ugol'noi have a higher carbon content than Anadyrya coals. They also have a higher hydrogen content and yield of initial resin. In several cases there was also a higher yield of volatile substances. Chukotka coals are characterized by a 10 percent higher initial resin yield than equally coalified Donetsk coals, other indicators were equal to those of Donetsk coals. Because of this, Chukotka coals are suitable for fuel in power plants and as raw materials in the chemical industry. (15 refs.) (In Russian)

  8. Effect of Recycle Solvent Hydrotreatment on Oil Yield of Direct Coal Liquefaction

    Directory of Open Access Journals (Sweden)

    Shansong Gao

    2015-07-01

    Full Text Available Effects of the recycle solvent hydrotreatment on oil yield of direct coal liquefaction were carried out in the 0.18 t/day direct coal liquefaction bench support unit of National Engineering Laboratory for Direct Coal Liquefaction (China. Results showed that the hydrogen-donating ability of the hydrogenated recycle solvent improved and the hydrogen consumption of solvent hydrotreatment was increased by decreasing liquid hourly space velocity (LHSV from 1.5 to 1.0 h−1 and increasing reaction pressure from 13.7 to 19.0 MPa. The hydrogen-donating ability of the hydrogenated recycle solvent was enhanced, thus promoting the oil yield and coal conversion of the liquefaction reaction. The coal conversion and distillates yield of coal liquefaction were increased from 88.74% to 88.82% and from 47.41% to 49.10%, respectively, with the increase in the solvent hydrotreatment pressure from 13.7 to 19.0 MPa. The coal conversion and distillates of coal liquefaction were increased from 88.82% to 89.27% and from 49.10% to 54.49%, respectively, when the LHSV decreased from 1.5 to 1.0 h−1 under the solvent hydrotreatment pressure of 19.0 MPa.

  9. Characterization of electrochemically deposited films from aqueous and ionic liquid cobalt precursors toward hydrogen evolution reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dushatinski, Thomas; Huff, Clay; Abdel-Fattah, Tarek M., E-mail: fattah@cnu.edu

    2016-11-01

    Highlights: • Co films deposition via aqueous and ionic liquid Precursors. • Hydrogen evolution produced from reactive surfaces. • Co deposited films characterized by SEM, AFM, EDX and XRD techniques. - Abstract: Electrodepositions of cobalt films were achieved using an aqueous or an ethylene glycol based non-aqueous solution containing choline chloride (vitamin B4) with cobalt chloride hexahydrate precursor toward hydrogen evolution reactions from sodium borohydride (NaBH{sub 4}) as solid hydrogen feedstock (SHF). The resulting cobalt films had reflectivity at 550 nm of 2.2% for aqueously deposited films (ACoF) and 1.3% for non-aqueously deposited films (NCoF). Surface morphology studied by scanning electron microscopy showed a positive correlation between particle size and thickness. The film thicknesses were tunable between >100 μm and <300 μm for each film. The roughness (Ra) value measurements by Dektak surface profiling showed that the NCoF (Ra = 165 nm) was smoother than the ACoF (Ra = 418 nm). The NCoFs and ACoFs contained only α phase (FCC) crystallites. The NCoFs were crystalline while the ACoFs were largely amorphous from X-ray diffraction analysis. The NCoF had an average Vickers hardness value of 84 MPa as compared to 176 MPa for ACoF. The aqueous precursor has a single absorption maximum at 510 nm and the non-aqueous precursor had three absorption maxima at 630, 670, and 695 nm. The hydrogen evolution reactions over a 1 cm{sup 2} catalytic surface with aqueous NaBH{sub 4} solutions generated rate constants (K) = equal to 4.9 × 10{sup −3} min{sup −1}, 4.6 × 10{sup −3} min{sup −1}, and 3.3 × 10{sup −3} min{sup −1} for ACoF, NCoF, and copper substrate respectively.

  10. Reaction rates and electrical resistivities of the hydrogen isotopes with, and their solubilities in, liquid lithium

    International Nuclear Information System (INIS)

    Pulham, R.J.; Adams, P.F.; Hubberstey, P.; Parry, G.; Thunder, A.E.

    1976-01-01

    The rate of reaction, k, of hydrogen and of deuterium with liquid lithium have been determined up to pressures of 20kNm -2 and at temperatures between 230 and 270 0 C. The reaction is first order with an apparent activation energy of 52.8 and 55.2 kJmol -1 for hydrogen and deuterium, respectively. The deuterium isotope effect, k/sub H/k/sub D/, decreases from 2.95 at 230 to 2.83 at 270 0 C. Tritium is predicted to react even more slowly than deuterium. The freezing point of lithium is depressed by 0.082 and 0.075 0 C, respectively, by dissolved hydride and deuteride giving eutectics at 0.016 mol percent H and 0.012 mol percent D in the metal-salt phase diagrams. The depression and eutectic concentration are expected to be less for tritium. The increase in the resistivity of liquid lithium caused by dissolved hydrogen isotopes is linear and relatively large, 5 x 10 -8 Ωm (mol percent H or D) -1 . The solubility of lithium hydride and deuteride was determined from the marked change in resistivity on saturation. The liquidus of the metal-salt phase diagram rises steeply from the eutectic point to meet the two-immiscible liquid region. Tritium is expected to be less soluble than deuterium. The partial molar enthalpies of solution are 44.2 and 55.0 kJmol -1 for hydrogen and deuterium, respectively. These values are used to calculate the solvation enthalpies of the isotope anions in the metal

  11. Magnetic field effects on geminate reactions. Study of anthraquinone - hydrogen donors systems

    International Nuclear Information System (INIS)

    Vidal, Marie-Helene

    1987-01-01

    This study is devoted to magnetic field effects on chemical reactions which involve a radical pair with correlated spins (radical in a 'cage'). In the first part, the radical pair theory is described: mechanisms of singlet-triplet mixing, the different interactions inside the pair and a quantum mechanical treatment of the radical pair. The details of the experimental method (nanosecond laser flash photolysis) are reported in the second part. In the third part are shown experimental results obtained on Anthraquinone (AQ) - Hydrogen donors systems: - There is no magnetic field effect in homogeneous solution even at a high viscosity. The absorption spectra of the different reaction intermediates are obtained. - However a magnetic field effect is put forward when AQ is introduced in SDS micelles which are hydrogen donors. The absorption spectrum of the AQH · . semi-quinone radical in 'cage' is shown and a mechanism is proposed for its disappearance to generate the AQH-S and AQH 2 species. - The addition of 9, 10 Dihydroanthracene (DH2) inside the micelle near AQ induces an increase of the magnetic field effect by creation of (AQH · . - DH · . ) pairs which diffuse slowly. - Fixed radical pairs in a protein matrix were studied in reaction centers of photosynthetic bacteria: in that case, the half effect field is shifted to low fields when compared to the previously described systems. (author) [fr

  12. Dodecahedral W@WC Composite as Efficient Catalyst for Hydrogen Evolution and Nitrobenzene Reduction Reactions.

    Science.gov (United States)

    Chen, Zhao-Yang; Duan, Long-Fa; Sheng, Tian; Lin, Xiao; Chen, Ya-Feng; Chu, You-Qun; Sun, Shi-Gang; Lin, Wen-Feng

    2017-06-21

    Core-shell composites with strong phase-phase contact could provide an incentive for catalytic activity. A simple, yet efficient, H 2 O-mediated method has been developed to synthesize a mesoscopic core-shell W@WC architecture with a dodecahedral microstructure, via a one-pot reaction. The H 2 O plays an important role in the resistance of carbon diffusion, resulting in the formation of the W core and W-terminated WC shell. Density functional theory (DFT) calculations reveal that adding W as core reduced the oxygen adsorption energy and provided the W-terminated WC surface. The W@WC exhibits significant electrocatalytic activities toward hydrogen evolution and nitrobenzene electroreduction reactions, which are comparable to those found for commercial Pt/C, and substantially higher than those found for meso- and nano-WC materials. The experimental results were explained by DFT calculations based on the energy profiles in the hydrogen evolution reactions over WC, W@WC, and Pt model surfaces. The W@WC also shows a high thermal stability and thus may serve as a promising more economical alternative to Pt catalysts in these important energy conversion and environmental protection applications. The current approach can also be extended or adapted to various metals and carbides, allowing for the design and fabrication of a wide range of catalytic and other multifunctional composites.

  13. Dehydriding reaction of Mg(NH2)2-LiH system under hydrogen pressure

    International Nuclear Information System (INIS)

    Aoki, M.; Noritake, T.; Kitahara, G.; Nakamori, Y.; Towata, S.; Orimo, S.

    2007-01-01

    The dehydriding and structural properties of the 3Mg(NH 2 ) 2 + 12LiH system under hydrogen pressure were investigated using the pressure-composition (p-c) isotherm measurement and X-ray diffraction (XRD) analysis. Two distinct regions, a plateau region and a sloping region, can be seen on the p-c isotherms and the amount of the desorbed hydrogen at 523 K was 4.9 mass%. The enthalpy of hydrogenation calculated using a van't Hoff plot was -46 kJ/mol H 2 . The dehydriding reaction was proposed for the 3Mg(NH 2 ) 2 + 12LiH system based on the obtained p-c isotherms and XRD profiles and chemical valences of Li, Mg, N, and H. In the plateau region on the p-c isotherm, Mg(NH 2 ) 2 , Li 4 Mg 3 (NH 2 ) 2 (NH) 4 (tetragonal), and LiH phases coexist and the molar ratio of the Li 4 Mg 3 (NH 2 ) 2 (NH) 4 phase increases (while those of Mg(NH 2 ) 2 and LiH phases decrease) with the amount of the desorbed hydrogen. On the other hand, the mixture of Li 4+x Mg 3 (NH 2 ) 2-x (NH) 4+x + (8-x)LiH (0 ≤ x ≤ 2) is formed and the lattice volume of the Li 4+x Mg 3 (NH 2 ) 2-x (NH) 4+x phase continuously increases with the amount of the desorbed hydrogen in the sloping region on the p-c isotherm

  14. Tritium-tracer study of catalytic hydrogenation reaction of ethylene on Ni, Pt and Ni-Pt

    International Nuclear Information System (INIS)

    Matsuyama, M.; Yasuda, Y.; Takeuchi, T.

    1978-01-01

    The influence of the pressure of tritiated hydrogen on the rate of the formation of tritiated ethylene, X, and that of tritiated ethane, Z, in the hydrogenation reaction of ethylene on Ni, Pt and Ni-Pt (1:1) alloy catalysts was investigated. The ratio of the rate of the exchange to that of the hydrogenation, selectivity X/Z, decreased markedly with the increase in the pressure of the tritiated hydrogen and the order of X/Z was Ni>Ni-Pt>Pt. These results were interpreted in terms of the difference in the amount of chemisorbed tritium on each metal catalyst. (orig.) [de

  15. Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

    Science.gov (United States)

    Niyitanga, Theophile; Jeong, Hae Kyung

    2018-05-01

    Molybdenum disulfide is a promising catalyst to replace the expensive platinum as an electrocatalyst but needs to be modified to present excellent electrocatalytic properties. Herein, we successfully modify molybdenum disulfide in methanol solvent for hydrogen evolution reaction by using a simple hydrothermal method. Overpotential reduced to -0.6 V from -1.5 V, and energy band gap decreased from 1.73 eV to 1.58 eV after the modification. The modified molybdenum disulfide also demonstrated lower resistance (42 Ω) at high frequency (1000 kHz) compared with that (240 Ω) of the precursor, showing that conductivity of the modified molybdenum disulfide has improved.

  16. Photo- and radiation-chemical stability of molecules. Reactions of monomolecular hydrogen atom splitting off

    International Nuclear Information System (INIS)

    Plotnikov, V.G.; Ovchinnikov, A.A.

    1978-01-01

    In the review of works published up to 1978 one of the main problems of radiation chemistry is discussed, namely the relationship between the structure of organic molecules and their resistance to the effect of ionizing radiation. Theoretical aspects of this problem are considered for reactions of monomolecular hydrogen atom splitting off. It is shown that the radical yield in low-temperature radiation-chemical experiments is connected with the position of lower triplet states of molecules, ionization potentials, polarity of medium and the energy of C-H bonds in cation radicals

  17. Factors responsible for activity of catalysts of different chemical types in the reaction of hydrogen oxidation

    International Nuclear Information System (INIS)

    Il'chenko, N.I.; Dolgikh, L.Yu.

    1985-01-01

    Reasons of differences in the kinetics and mechanism of the H 2 oxidation on optimum metallic (Pt), carbide (WC) and oxide (Co 3 O 4 ) catalysts are discussed. These differences lead to unequal specific activity. It is shown that the catalytic activity of the catalysts in question increases with respect to reactions of isotopic exchange and hydrogen oxidation with an increasing electron-donating ability of anat of the transition metal M on which H 2 is adsorbed. The possibility is considered of increasing the transition metal activity by introduction of additions to increase the electron-donating ability of M

  18. Main component analysis of nuclear magnetic resonance /sup 1/H and /sup 13/C quantitative spectra of hydrogenation products of tars from Kansk-Achinsk Achinsk and Cheremkhovsk coals

    Energy Technology Data Exchange (ETDEWEB)

    Kushnarev, D.F.; Polonov, V.M.; Donskikh, V.I.; Rokhina, E.F.; Kalabin, G.A.

    1986-03-01

    Possibility is discussed of examining nuclear magnetic resonance /sup 1/H and /sup 13/C quantitative spectra of coal tar hydrogenation products using main component factorial analysis and applying special mathematical methods of processing experimental data. Nuclear magnetic resonance spectra of hydrogenation products of low temperature Cheremkhovsk coal carbonization tar and rapid pyrolysis Kansk-Achinsk coal tar were obtained on a WP-200SY (Bruker) spectrometer at 50.3 and 200.1 MHz, respectively. Data processing was carried out on an ODRA-1304 computer. Comparative correlation of parameters are given of tars and hydrogenation products which consist of hydrogenation of aromatic cycles and destruction of alkyl substituents, and factorial loads on structural parameters of tar hydrogenation products. 11 references.

  19. Report for the coal type committee in fiscal 1992; 1992 nendo tanshu iinkai hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1993-03-01

    This paper reports the activities of the coal type committee in fiscal 1992, and summarizes the main technological achievements. In the Chinese coal liquefaction test, fiscal 1991 has performed liquefaction tests on Fushun coal by using a small continuous testing facility (0.1 t/d) at the Coal Chemistry Research Institute in Beijing. Fiscal 1992 has completed the liquefaction tests on Shengli coal. In October, a liquefaction test was carried out by using Tianzhu coal according to the NEDOL process. This paper reports the result of the liquefaction test on the Shengli coal, and the result of the analysis on the Fushun coal liquefied oil. The coal type selection and investigation having been performed to date reveals close correlation among the maceral composition of coal, coal rank and liquefied oil yield. Coals having good reactivity and suitable for liquefaction are generally suitable also for gasification. In the pretreatment of coal as a gasification material for hydrogen manufacture, a test was performed by using A heavy oil and tar sand bitumen plus A heavy oil as the granulating agents. With Montana coal, the highest de-ashing rate was achieved when the oil was added at 35% by weight. Both of the reaction rate and oil yield were improved. A handling test was carried out up to 72.5 degrees C, wherein Tatung coal presented no problems in both of the discharging and sticking tendencies. (NEDO)

  20. A Reduced Reaction Scheme for Volatile Nitrogen Conversion in Coal Combustion

    DEFF Research Database (Denmark)

    Pedersen, Lars Saaby; Glarborg, Peter; Dam-Johansen, Kim

    1998-01-01

    In pulverised coal flames, the most important volatile nitrogen component forming NOx is HCN. To be able to model the nitrogen chemistry in coal flames it is necessary to have an adequate model for HCN oxidation. The present work was concerned with developing a model for HCN/NH3/NO conversion based...... that the CO/H-2 chemistry was described adequately, the reduced HCN/NH3/NO model compared very well with the detailed model over a wide range of stoichiometries. Decoupling of the HCN chemistry from the CO/H-2 chemistry resulted in over-prediction of the HCN oxidation rate under fuel rich conditions, but had...... negligible effect on the CO/H-2 chemistry. Comparison with simplified HCN models from the literature revealed significant differences, indicating that these models should be used cautiously in modelling volatile nitrogen conversion....

  1. Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions

    Energy Technology Data Exchange (ETDEWEB)

    Arenillas, A.; Rubiera, F.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Oviedo (Spain)

    2002-12-15

    Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with on-line battery of analyzers. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behaviour in other combustion equipments, i.e. fluidized bed combustors. It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range NO heterogeneous reduction seems to be controlled by the evolution of surface complexes. In the high-temperature range a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor. 27 refs., 6 figs., 1 tab.

  2. Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Redman, Daniel W; Rose, Michael J; Stevenson, Keith J

    2017-09-19

    This work reports on the general electrodeposition mechanism of tetrachalcogenmetallates from 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Both tetrathio- and tetraselenomolybdate underwent anodic electrodeposition and cathodic corrosion reactions as determined by UV-vis spectroelectrochemistry. Electrodeposition was carried out by cycling the potential between the anodic and cathodic regimes. This resulted in a film of densely packed nanoparticles of amorphous MoS x or MoSe x as determined by SEM, Raman, and XPS. The films were shown to have high activity for the hydrogen evolution reaction. The onset potential (J = 1 mA/cm 2 ) of the MoS x film was E = -0.208 V vs RHE, and that of MoSe x was E = -0.230 V vs RHE. The Tafel slope of MoS x was 42 mV/decade, and that of MoSe x was 59 mV/decade.

  3. On the influence of hydronium and hydroxide ion diffusion on the hydrogen and oxygen evolution reactions in aqueous media

    DEFF Research Database (Denmark)

    Wiberg, Gustav Karl Henrik; Arenz, Matthias

    2015-01-01

    We present a study concerning the influence of the diffusion of H+ and OH- ions on the hydrogen and oxygen evolution reactions (HER and OER) in aqueous electrolyte solutions. Using a rotating disk electrode (RDE), it is shown that at certain conditions the observed current, i.e., the reaction rate...

  4. In Vivo Lighted Fluorescence via Fenton Reaction: Approach for Imaging of Hydrogen Peroxide in Living Systems.

    Science.gov (United States)

    Liu, Changhui; Chen, Weiju; Qing, Zhihe; Zheng, Jing; Xiao, Yue; Yang, Sheng; Wang, Lili; Li, Yinhui; Yang, Ronghua

    2016-04-05

    By virtue of its high sensitivity and rapidity, Fenton reaction has been demonstrated as a powerful tool for in vitro biochemical analysis; however, in vivo applications of Fenton reaction still remain to be exploited. Herein, we report, for the first time, the design, formation and testing of Fenton reaction for in vivo fluorescence imaging of hydrogen peroxide (H2O2). To realize in vivo fluorescence imaging of H2O2 via Fenton reaction, a functional nanosphere, Fc@MSN-FDNA/PTAD, is fabricated from mesoporous silica nanoparticle (MSN), a Fenton reagent of ferrocene (Fc), ROX-labeled DNA (FDNA), and a cationic perylene derivative (PTAD). The ferrocene molecules are locked in the pore entrances of MSN, and exterior of MSN is covalently immobilized with FDNA. As a key part, PTAD acts as not only the gatekeeper of MSN but also the efficient quencher of ROX. H2O2 can permeate into the nanosphere and react with ferrocene to product hydroxyl radical (·OH) via Fenton reaction, which cleaves FDNA to detach ROX from PTAD, thus in turn, lights the ROX fluorescence. Under physiological condition, H2O2 can be determined from 5.0 nM to 1.0 μM with a detection limit of 2.4 nM. Because of the rapid kinetics of Fenton reaction and high specificity for H2O2, the proposed method meets the requirement for real applications. The feasibility of Fc@MSN-FDNA/PTAD for in vivo applications is demonstrated for fluorescence imaging of exogenous and endogenous H2O2 in cells and mice. We expect that this work will not only contribute to the H2O2-releated studies but also open up a new way to exploit in vivo Fenton reaction for biochemical research.

  5. Hydrodeoxygenation of coal using organometallic catalyst precursors

    Science.gov (United States)

    Kirby, Stephen R.

    2002-04-01

    The objective of this dissertation was to determine the desirability of organometallic compounds for the hydrodeoxygenation (HDO) of coal during liquefaction. The primary focus of this study was the removal of phenol-like compounds from coal liquids for the production of a thermally stable jet fuel. Investigation of the HDO ability of an organometallic compound containing both cobalt and molybdenum (CoMo-T2) was achieved using a combination of model compound and coal experiments. Model compounds were chosen representing four oxygen functional groups present in a range of coals. Electron density and bond order calculations were performed for anthrone, dinaphthyl ether, xanthene, di-t-butylmethylphenol, and some of their derivatives to ascertain a potential order of hydrogenolysis and hydrogenation reactivity for these compounds. The four model compounds were then reacted with CoMo-T2, as well as ammonium tetrathiomolybdate (ATTM). Products of reaction were grouped as compounds that had undergone deoxygenation, those that had aromatic rings reduced, those that were products of both reaction pathways, and those produced through other routes. ATTM had an affinity for both reaction types. Its reaction order for the four model compounds with respect to deoxygenated compounds was the same as that estimated from electron density calculations for hydrogenolysis reactivity. CoMo-T2 appeared to show a preference toward hydrogenation, although deoxygenated products were still achieved in similar, or greater, yields, for almost all the model compounds. The reactivity order achieved for the four compounds with CoMo-T2 was similar to that estimated from bond order calculations for hydrogenation reactivity. Three coals were selected representing a range of coal ranks and oxygen contents. DECS-26 (Wyodak), DECS-24 (Illinois #6), and DECS-23 (Pittsburgh #8) were analyzed by CPMAS 13C NMR and pyrolysis-GC-MS to determine the functional groups comprising the oxygen content of these

  6. Understanding the reaction between muonium atoms and hydrogen molecules: zero point energy, tunnelling, and vibrational adiabaticity

    Science.gov (United States)

    Aldegunde, J.; Jambrina, P. G.; García, E.; Herrero, V. J.; Sáez-Rábanos, V.; Aoiz, F. J.

    2013-11-01

    The advent of very precise measurements of rate coefficients in reactions of muonium (Mu), the lightest hydrogen isotope, with H2 in its ground and first vibrational state and of kinetic isotope effects with respect to heavier isotopes has triggered a renewed interests in the field of muonic chemistry. The aim of the present article is to review the most recent results about the dynamics and mechanism of the reaction Mu+H2 to shed light on the importance of quantum effects such as tunnelling, the preservation of the zero point energy, and the vibrational adiabaticity. In addition to accurate quantum mechanical (QM) calculations, quasiclassical trajectories (QCT) have been run in order to check the reliability of this method for this isotopic variant. It has been found that the reaction with H2(v=0) is dominated by the high zero point energy (ZPE) of the products and that tunnelling is largely irrelevant. Accordingly, both QCT calculations that preserve the products' ZPE as well as those based on the Ring Polymer Molecular Dynamics methodology can reproduce the QM rate coefficients. However, when the hydrogen molecule is vibrationally excited, QCT calculations fail completely in the prediction of the huge vibrational enhancement of the reactivity. This failure is attributed to tunnelling, which plays a decisive role breaking the vibrational adiabaticity when v=1. By means of the analysis of the results, it can be concluded that the tunnelling takes place through the ν1=1 collinear barrier. Somehow, the tunnelling that is missing in the Mu+H2(v=0) reaction is found in Mu+H2(v=1).

  7. Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

    Science.gov (United States)

    Yuan, Heyang; He, Zhen

    2017-07-01

    Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.

    2015-10-20

    Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.

  9. When hydroquinone meets methoxy radical: Hydrogen abstraction reaction from the viewpoint of interacting quantum atoms.

    Science.gov (United States)

    Petković, Milena; Nakarada, Đura; Etinski, Mihajlo

    2018-05-25

    Interacting Quantum Atoms methodology is used for a detailed analysis of hydrogen abstraction reaction from hydroquinone by methoxy radical. Two pathways are analyzed, which differ in the orientation of the reactants at the corresponding transition states. Although the discrepancy between the two barriers amounts to only 2 kJ/mol, which implies that the two pathways are of comparable probability, the extent of intra-atomic and inter-atomic energy changes differs considerably. We thus demonstrated that Interacting Quantum Atoms procedure can be applied to unravel distinct energy transfer routes in seemingly similar mechanisms. Identification of energy components with the greatest contribution to the variation of the overall energy (intra-atomic and inter-atomic terms that involve hydroquinone's oxygen and the carbon atom covalently bound to it, the transferring hydrogen and methoxy radical's oxygen), is performed using the Relative energy gradient method. Additionally, the Interacting Quantum Fragments approach shed light on the nature of dominant interactions among selected fragments: both Coulomb and exchange-correlation contributions are of comparable importance when considering interactions of the transferring hydrogen atom with all other atoms, whereas the exchange-correlation term dominates interaction between methoxy radical's methyl group and hydroquinone's aromatic ring. This study represents one of the first applications of Interacting Quantum Fragments approach on first order saddle points. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

  10. Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.; Manjunath, K.; Samrat, D.; Reddy, Viswanath; Ramakrishnappa, T.; Nagaraju, Doddahalli H.

    2015-01-01

    Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.

  11. Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

    Directory of Open Access Journals (Sweden)

    Yasuharu Kanda

    2018-04-01

    Full Text Available In this work, the development of a highly active noble metal phosphide (NMXPY-based hydrodesulfurization (HDS catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT, the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering.

  12. Thermogravimetric analysis of multi-stage hydropyrolysis of different coals

    Energy Technology Data Exchange (ETDEWEB)

    Li, W.; Wang, N.; Li, B [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion

    2001-09-01

    Based on the characteristic of hydropyrolysis (HyPy), a multi-stage MHyPy of different coals was investigated using thermogravimetry. The results show that keeping the near peak temperature for some time in HyPy process can obviously increase the conversion rate, which is believed due to the full match between formation rate of free radicals and supply of hydrogen. The fast heating in MHyPy process results in the same conversion rate as that of the slow heating in HyPy process, which leads to the less reaction time and high yield of oil. The effect of MHyPy depends on the coal structure itself and it is notable for the coal with high H/C ratio. This suggests that the external hydrogen promotes the reaction between intrinsic hydrogen and free radicals. The MHyPy improves the removal of sulfur and nitrogen. 5 refs., 7 figs., 2 tabs.

  13. Hydrogen sulfide removal from hot coal gas by various mesoporous silica supported Mn2O3 sorbents

    International Nuclear Information System (INIS)

    Zhang, Z.F.; Liu, B.S.; Wang, F.; Wang, W.S.; Xia, C.; Zheng, S.; Amin, R.

    2014-01-01

    Graphical abstract: - Highlights: • Mn 2 O 3 /KIT-1 presented the best desulfurization performance at 600–850 °C. • High sulfur capacity of Mn 2 O 3 /KIT-1 correlated closely with 3-D channel of KIT-1. • Desulfurization character depended strongly on framework structure of sorbents. • High steam content suppressed greatly the occurrence of sulfidation reaction. - Abstract: A series of 50 wt% Mn 2 O 3 sorbents was prepared using various mesoporous silica, MCM-41, HMS, and KIT-1 as support. The influence of textural parameters of mesoporous silica, especially type of channel on the desulfurization performance of Mn 2 O 3 sorbents was investigated at 600–850 °C using hot coal gas containing 0.33 vol.% H 2 S. The fresh and used sorbents were characterized by means of N 2 -adsorption, x-ray diffraction (XRD), high resolution transmission microscopy (HRTEM) and H 2 temperature- programmed reduction (H 2 -TPR) techniques. The results confirmed that the manganese oxide was dispersed highly in regular pore channel of the mesoporous supports due to high surface area. Compared with the Mn 2 O 3 /diatomite, all mesoporous silica supported Mn 2 O 3 sorbents exhibited high breakthrough sulfur capacity and a sharp deactivation rate after the breakthrough point. Compared to Mn 2 O 3 /MCM-41 and Mn 2 O 3 /HMS sorbent, the Mn 2 O 3 /KIT-1 showed better desulfurization performance because of the 3D wormhole-like channel. The high sulfur capacity of the Mn 2 O 3 /KIT-1 sorbent was maintained during the eight consecutive desulfurization-regeneration cycles. The Mn 2 O 3 /KIT-1 still presented high desulfurization activity when hot coal gas contained low steam (<5%)

  14. Role of non-ferrous coal minerals and by-product metallic wastes in coal liquefaction. Technical progress report, December 1, 1980-February 28, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Garg, D.; Givens, E.N.; Schweighardt, F.K.; Curtis, C.W.; Guin, J.A.; Huang, W.J.; Shridharani, K.

    1981-04-01

    Results from screening studies showed that the pyrite samples separated from various coal seams had similar catalytic activity. The addition of all the pyrite samples to feed slurry increased conversion of coal and production of oil. A sample of fusinite was also tested for its liquefaction behavior with and without added pyrite. The addition of pyrite increased the conversion of fusinite and production of oil. These results show that pyrite catalyzes the conversion of fusinite and therefore improves overall coal conversion. Conversion of coal and oil production increased by impregnating coal with iron and molybdenum compounds. Coal conversion and oil production also increased with increasing concentration of both iron and molybdenum impregnated on coal. Addition of various transition metal sulfides increased coal conversion and oil production. Dramatic improvements were noted with nickel, vanadium, and tin sulfides. Addition of transition metal naphthenates produced mixed results; some of them improved coal conversion and others had no effect. The effect of metal concentration on coal conversion was also not clear. Deep cleaning of coal did not affect coal conversion, but it significantly reduced oil production. Addition of pyrite separated from coal to deep cleaned coal sample regained the oil production to the original value, i.e., oil produced from liquefaction of raw coal.Coal cleaned by oil agglomeration gave highest coal conversion and oil production. Basic and non-basic nitrogen compounds reduced the naphthalene hydrogenation activity of both Co-Mo-Al and sulfided Fe/sub 2/O/sub 3/. Sulfided Fe/sub 2/O/sub 3/ was inactive for denitrogenation of quinoline, and the reaction product mainly consisted of hydrogenated and hydrocracked quinoline. On the contrary, Co-Mo-Al was active for denitrogenation of quinoline, resulting in lower quinoline poisoning.

  15. FY 1980 Report on results of Sunshine Project by Coal Group. Basic researches on coal liquefaction techniques by solvolysis; 1980 nendo sunshine keikaku sekitanhan hokokusho. Sekitan no solvolysis ekika gijutsu no kiso kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1981-07-01

    The basic experimental researches were carried out for coal liquefaction by solvolysis. The studied items include hydrogenation conditions for treating the primary liquefied products, asphalt, pitch and model solvents (e.g., anthracene oil) in the presence of a commercial catalyst, solvolysis conditions for finely divided, molten coal using a hydrogenation recycled solvent, hydrotreating solvents, analysis of solvolysis-liquefied products, and liquefaction capacity of fractionated solvents for finely divided, molten coal. The studied items for separation of minerals include settlement at high temperature of the solid residue from the first liquefaction stage, and changed coal particle size distribution as a result of the first-stage liquefaction reactions in the presence of a hydrogenation solvent. The experimental study results indicate that conversion of finely divided molten coal into asphaltenes and preasphaltenes is notably accelerated in the phase-II coal liquefaction process by solvolysis, when a hydrotreating solvent is used for the first stage solvolysis process. (NEDO)

  16. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    International Nuclear Information System (INIS)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-01

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  17. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-29

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  18. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

    Science.gov (United States)

    Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

    2016-09-19

    Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

    International Nuclear Information System (INIS)

    Sato, S.

    1987-01-01

    Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

  20. Methylation reactions, the redox balance and atherothrombosis: the search for a link with hydrogen sulfide.

    Science.gov (United States)

    Lupoli, Roberta; Di Minno, Alessandro; Spadarella, Gaia; Franchini, Massimo; Sorrentino, Raffaella; Cirino, Giuseppe; Di Minno, Giovanni

    2015-06-01

    It is now clear that homocysteine (Hcy) is irreversibly degraded to hydrogen sulfide (H(2)S), an endogenous gasotransmitter that causes in vivo platelet activation via upregulation of phospholipase A2 and downstream boost of the arachidonate cascade. This mechanism involves a transsulfuration pathway. Based on these new data, clinical and experimental models on the relationships between Hcy and folate pathways in vascular disease and information on the Hcy controversy have been reanalyzed in the present review. Most interventional trials focused on Hcy lowering by folate administration did not exclude patients routinely taking the arachidonate inhibitor aspirin. This may have influenced the results of some of these trials. It is also clear that nutritional intake of folate affects several enzymatic reactions of the methionine-Hcy cycle and associated one-carbon metabolism and, thereby, both methylation reactions and redox balance. Hence, it is conceivable that the abnormally high Hcy levels seen in pathologic states reflect a poorly elucidated perturbation of such reactions and of such balance. While it is unknown whether there is an interplay between H2S, methylation reactions, and redox balance, measuring the sole reduction of blood Hcy that follows folate administration may well be an oversimplified approach to a complex biologic perturbation. The need to investigate this complex framework is thoroughly discussed in this article. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

  1. Mechanism and kinetics of the electrocatalytic reaction responsible for the high cost of hydrogen fuel cells.

    Science.gov (United States)

    Cheng, Tao; Goddard, William A; An, Qi; Xiao, Hai; Merinov, Boris; Morozov, Sergey

    2017-01-25

    The sluggish oxygen reduction reaction (ORR) is a major impediment to the economic use of hydrogen fuel cells in transportation. In this work, we report the full ORR reaction mechanism for Pt(111) based on Quantum Mechanics (QM) based Reactive metadynamics (RμD) simulations including explicit water to obtain free energy reaction barriers at 298 K. The lowest energy pathway for 4 e - water formation is: first, *OOH formation; second, *OOH reduction to H 2 O and O*; third, O* hydrolysis using surface water to produce two *OH and finally *OH hydration to water. Water formation is the rate-determining step (RDS) for potentials above 0.87 Volt, the normal operating range. Considering the Eley-Rideal (ER) mechanism involving protons from the solvent, we predict the free energy reaction barrier at 298 K for water formation to be 0.25 eV for an external potential below U = 0.87 V and 0.41 eV at U = 1.23 V, in good agreement with experimental values of 0.22 eV and 0.44 eV, respectively. With the mechanism now fully understood, we can use this now validated methodology to examine the changes upon alloying and surface modifications to increase the rate by reducing the barrier for water formation.

  2. Gasification catalysts prepared by the reaction of CaCO3 and coal. Tansan karushiumu to sekitan no ion kokan hanno ni yori choseishita kokassei gas ka shokubai

    Energy Technology Data Exchange (ETDEWEB)

    Otsuka, Y.; Asami, K. (Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science)

    1991-11-07

    Properties of the active gasification catalysts prepared by ion exchange reaction of CaCO3 and coal were studied. Several kinds of Ca-loaded coal specimens were prepared to compare their properties among them by physically mixing coal particles with CaCO3 ones in air, by kneading both materials in pure water while crashing and by impregnating CaCO3 into coal while agitating them in pure water. Although Ca-loading onto the impregnated specimen was nearly one-half that of the kneaded one, its catalysis was equal to the kneaded one. CaCO3 greatly accelerated steam gasification only by mixing it with low rank coal in water, and such a high catalytic activity was caused by ion-exchanged Ca produced by the reaction between CaCO3 and COOH radical in coal. Aragonite of seashells yielded more Ca-loading than calcite of limestone, suggesting one of the useful treatment of seashell waste. 3 refs., 4 figs., 2 tabs.

  3. Studies on the catalysts for coal liquefaction. ; Specific behaviours of coals of different ranks in their hydrogenolysis reactions catalyzed by various kinds of catalysts. Sekitan ekikayo shokubai ni kansuru kenkyu. ; Suisoka bunkai seiseibutsu sosei ni oyobosu kakushu shokubai no koka

    Energy Technology Data Exchange (ETDEWEB)

    Takechi, Y; Ikenaga, N; Oda, H; Yokokawa, C [Kansai University, Osaka (Japan). Faculty of Engineering

    1991-11-07

    Three kinds of coals with different rank of 76, 85 and 87C% were hydrocracked to study the specific reaction behavior of four kinds of 1coal liquefaction catalysts such as CuCrO4, Fe2O3+S, MoO3-TiO2 and MoS3-Al2O3. The reaction was conducted without any solvent to find out the specific phenomenon of each combination of coal and catalyst, and terminated at the point where nearly 30% of an initial amount of coal is converted to benzene-soluble. The products were separated by GPC into four fractions, and their average molecular weights and intrinsic viscosities were measured to study characteristics of each combination. As a result, the molecular weight distribution was obviously dependent on the combination of coal and catalyst, and no specific relation was observed between the molecular weight and intrinsic viscosity. The molecular of each fraction had a bar shape with an elliptic section indicating no apparent correlation with the molecular weight. 3 refs., 1 figs., 2 tabs.

  4. The hydrogen atom-deuterium molecule reaction: Experimental determination of product quantum state distributions

    International Nuclear Information System (INIS)

    Rinnen, K.

    1989-01-01

    The H + H 2 atom exchange reaction (and its isotopic analogs) is the simplest neutral bimolecular chemical reaction because of the small number of electrons in the system and the lightness of the nuclei. The H 3 potential energy surface (PES) is the most accurately known reactive surface (LSTH surface); there have been both quasiclassical trajectory (QCT) and quantal calculations performed on it. This is one of the few systems for which theory is ahead of experiment, and many theoretical predictions await experimental comparison. The H + D 2 → HD + D reaction is studied using thermal D 2 (∼298 K) and translationally hot hydrogen atoms. Photolysis of HI at 266 nm generates H atoms with center-of-mass collision energies of 1.3 and 0.55 eV, both of which are above the classical reaction barrier of 0.42 eV. The rovibrational population distribution of the molecular product is measured by (2+1) resonance-enhanced multiphoton ionization (REMPI). A major effort has been directed toward calibrating the (2+1) REMPI detection procedure, to determine quantitatively the relationship between ion signals and relative quantum state populations for HD. An effusive, high-temperature nozzle has been constructed to populate thermally the high rovibrational levels observed in the reaction. The results are compared to theoretical calculations of the E,F 1 Σ g + - X 1 Σ g + two-photon transition moments. For the H + D 2 reaction, the populations of all energetically accessible HD product levels are measured. Specifically, the following levels are observed: HD(v = 0, J = 0-15), HD(v = 1, J = 0-12), and HD(v = 2, J = 0-8). Of the available energy, 73% is partitioned into product translation, 18% into HD rotation, and 9% into HD vibration

  5. REGULATION OF COAL POLYMER DEGRADATION BY FUNGI

    Energy Technology Data Exchange (ETDEWEB)

    John A. Bumpus

    1998-11-30

    A variety of lignin degrading fungi mediate solubilization and subsequent biodegradation of coal macromolecules (a.k.a. coal polymer) from highly oxidized low rank coals such as leonardites. It appears that oxalate or possibly other metal chelators (i.e., certain Krebs Cycle intermediates) mediate solubilization of low rank coals while extracellular oxidases have a role in subsequent oxidation of solubilized coal macromolecule. These processes are under nutritional control. For example, in the case of P. chrysosporium, solubilization of leonardite occurred when the fungi were cultured on most but not all nutrient agars tested and subsequent biodegradation occurred only in nutrient nitrogen limited cultures. Lignin peroxidases mediate oxidation of coal macromolecule in a reaction that is dependent on the presence of veratryl alcohol and hydrogen peroxide. Kinetic evidence suggests that veratryl alcohol is oxidized to the veratryl alcohol cation radical which then mediates oxidation of the coal macromolecule. Results by others suggest that Mn peroxidases mediate formation of reactive Mn{sup 3+} complexes which also mediate oxidation of coal macromolecule. A biomimetic approach was used to study solubilization of a North Dakota leonardite. It was found that a concentration {approximately}75 mM sodium oxalate was optimal for solubilization of this low rank coal. This is important because this is well above the concentration of oxalate produced by fungi in liquid culture. Higher local concentrations probably occur in solid agar cultures and thus may account for the observation that greater solubilization occurs in agar media relative to liquid media. The characteristics of biomimetically solubilized leonardite were similar to those of biologically solubilized leonardite. Perhaps our most interesting observation was that in addition to oxalate, other common Lewis bases (phosphate/hydrogen phosphate/dihydrogen phosphate and bicarbonate/carbonate ions) are able to mediate

  6. High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

    Science.gov (United States)

    Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

    2018-02-26

    The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

  7. Thermal behaviour during the pyrolysis of low rank perhydrous coals

    Energy Technology Data Exchange (ETDEWEB)

    Arenillas, A.; Rubiera, F.; Pis, J.J.; Cuesta, M.J.; Suarez-Ruiz, I. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain); Iglesias, M.J. [Area de Quimica Organica, Universidad de Almeria, Carretera de Sacramento, 04120 Almeria (Spain); Jimenez, A. [Area de Cristalografia y Mineralogia, Departamento de Geologia, Campus de Llamaquique, 33005 Oviedo (Spain)

    2003-08-01

    Perhydrous coals are characterised by high H/C atomic ratios and so their chemical structure is substantially modified with respect to that of conventional coals. As a result, perhydrous coals show different physico-chemical properties to common coals (i.e. higher volatile matter content, enhancement of oil/tar potential, relatively lower porosity and higher fluidity during carbonisation). However, there is little information about thermal behaviour during the pyrolysis of this type of coal. In this work, six perhydrous coals (H/C ratio between 0.83 and 1.07) were pyrolysed and analysed by simultaneous thermogravimetry/mass spectrometry. The results of this work have revealed the influence of high H/C values on the thermal behaviour of the coals studied. During pyrolysis the perhydrous coals exhibit very well defined, symmetrical peaks in the mass loss rate profiles, while normal coals usually show a broader peak. The shape of such curves suggests that in perhydrous coals fragmentation processes prevailed over condensation reactions. The high hydrogen content of perhydrous coals may stabilise the free radicals formed during heat treatment, increasing the production of light components.

  8. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

    2017-11-21

    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  9. Anomalous deuteron to hydrogen ratio in naturally occuring fission reactions and the possibility of deuteron disintegration

    International Nuclear Information System (INIS)

    Shaheen, M.; Ragheb, M.

    1992-01-01

    A hypothesis is presented for explaining the experimentally determined anomalous D/H ratio observed in the samples from the naturally occuring fission reaction in the Oklo phenomenon. No other explanation has been given, to the best knowledge, for the large difference between the measured D/H ratio in the Oklo samples and the expected values in a fission neutron spectrum. A multicomponent system consisting of hydrogen, deuterium, tritium and helium nuclei is considered. An analytical solution is derived and solved using as boundary conditions the experimentally determined value of the D/H ratio. The solution of the rate equations for hydrogen and deuteron concentrations, assuming a pure fission process without a deuteron sink term, yields a D/H ratio of 445 ppm for a reaction in which the fluence of neutrons is 10 21 n/cm 2 . This exceeds the experimentally observed value of 127 ppm, and the naturally occuring value of 150 ppm. Solving the same rate equations accounting for a deuterium sink term using a hypothesis of deuteron disintegration, and the experimentally observed value of 127 ppm yields a deuteron disintegration constant of 7.47*10 -14 s -1 . Deuteron disintegration would provide a neutron source, in addition to the fission neutrons, driving a subcritical chain reaction over an extended period of time. Relationship of the presented hypothesis to the Vlasov theory of an annihilation meteorite impact explosion explaining the experimentally observed anomalous 235 U/ 238 U ratio, and to the suggestion of deuteron disintegration as a possible explanation of some observations of deuterium dissociation in palladium and titanium electrodes is discussed. The tritium andhelium-3 rate equations are further solved under the deuteron disintegration hypothesis and the relationship of the present work to the work by JONES et al. is discussed. (author) 16 refs.; 7 figs.; 2 tabs

  10. Material balance in coal. 2. Oxygen determination and stoichiometry of 33 coals

    International Nuclear Information System (INIS)

    Volborth, A.; Miller, G.E.; Garner, C.K.; Jerabek, P.A.

    1977-01-01

    The chemical analysis of coal can be supplemented by the determination of oxygen in high and low temperature ash, in coal as received and in coal dried at 105 0 C. The rapid method utilizes fast-neutron activation. The reaction 16 O(n,p) 16 N and counting of the 6.1 and 7.1 MeV gammas of 7.3 second half-life are used. A specially designed dual transfer and simultaneous counting system gives very accurate results. Oxygen in 33 coals ranging from lignite to low volatile bituminous coal is determined and compared with ''oxygen by difference.'' Considerable discrepancies are observed. Better stoichiometric results are obtained if oxygen in coal ash, in wet coal and in the dried coal is determined. This permits the estimation of the true material balances using data of the ultimate and the proximate coal analysis. The oxygen determination provides the coal chemist with an accurate basis and can be used to rank coal. The summation of the percent of carbon, nitrogen, hydrogen, sulfur, and oxygen becomes more meaningful and some errors can be detected and the state of completeness of coal analysis thus evaluated. Total sulfur can be estimated and oxidation effects during drying can be detected. These affect the moisture determination. It appears that after more data are collected, the interpretation of solid fuel analyses may be facilitated and will be stoichiometrically more meaningful. It is shown that it may be possible to simplify the present time-consuming methods of coal analysis

  11. Partial Oxidation Gas Turbine for Power and Hydrogen Co-Production from Coal-Derived Fuel in Industrial Applications

    Energy Technology Data Exchange (ETDEWEB)

    Joseph Rabovitser

    2009-06-30

    , pressures, and volumetric flows practically identical. In POGT mode, the turbine specific power (turbine net power per lb mass flow from expander exhaust) is twice the value of the onventional turbine. POGT based IGCC plant conceptual design was developed and major components have been identified. Fuel flexible fluid bed gasifier, and novel POGT unit are the key components of the 100 MW IGCC plant for co producing electricity, hydrogen and/or yngas. Plant performances were calculated for bituminous coal and oxygen blown versions. Various POGT based, natural gas fueled systems for production of electricity only, coproduction of electricity and hydrogen, and co production of electricity and syngas for gas to liquid and hemical processes were developed and evaluated. Performance calculations for several versions of these systems were conducted. 64.6 % LHV efficiency for fuel to electricity in combined cycle was achieved. Such a high efficiency arise from using of syngas from POGT exhaust s a fuel that can provide required temperature level for superheated steam generation in HRSG, as well as combustion air preheating. Studies of POGT materials and combustion instabilities in POR were conducted and results reported. Preliminary market assessment was performed, and recommendations for POGT systems applications in oil industry were defined. POGT technology is ready to proceed to the engineering prototype stage, which is recommended.

  12. Characterisation of model compounds and a synthetic coal by TG/MS/FTIR to represent the pyrolysis behaviour of coal

    Energy Technology Data Exchange (ETDEWEB)

    Arenillas, A.; Pevida, C.; Rubiera, F.; Garcia, R.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain)

    2004-06-01

    Coal pyrolysis is the initial, accompanying reaction of a number of coal conversion processes such as hydrogenation, combustion and gasification. However, because of the inherent complexity of coal composition, it is difficult to describe coal pyrolysis clearly. Single model compounds have been used before in order to provide additional insight into the complex processes that occur in the pyrolysis of coal. Yet the picture obtained is a simplified one and certain important aspects such as coal structure, interactions between different surface groups and cross-links are omitted. The approach used in this work involves the preparation of a synthetic coal, SC, with a known structure by curing a mixture of single, well-defined model compounds. By means of chemical characterisation, the SC was shown to contain the macroscopic features of a high volatile coal (proximate and ultimate analyses). FTIR characterisation revealed the presence of functional groups similar to those of coal in the structure of the SC. Temperature-programmed pyrolysis tests were performed in a thermobalance linked to a mass spectrometer and a Fourier transform infrared analyser (TG/MS/FTIR). The thermal behaviour of the synthetic coal (i.e., rate of mass loss and the evolution profiles of gaseous compounds during pyrolysis tests) is very similar to that of the high volatile bituminous coal which was used as a reference material. The great advantage of using SC lies in the fact that its composition and structure can be accurately determined and employed in subsequent applications in basic and mechanistic studies.

  13. Evidence of 9Be  +  p nuclear reactions during 2ω CH and hydrogen minority ICRH in JET-ILW hydrogen and deuterium plasmas

    Science.gov (United States)

    Krasilnikov, A. V.; Kiptily, V.; Lerche, E.; Van Eester, D.; Afanasyev, V. I.; Giroud, C.; Goloborodko, V.; Hellesen, C.; Popovichev, S. V.; Mironov, M. I.; contributors, JET

    2018-02-01

    The intensity of 9Be  +  p nuclear fusion reactions was experimentally studied during second harmonic (2ω CH) ion-cyclotron resonance heating (ICRH) and further analyzed during fundamental hydrogen minority ICRH of JET-ILW hydrogen and deuterium plasmas. In relatively low-density plasmas with a high ICRH power, a population of fast H+ ions was created and measured by neutral particle analyzers. Primary and secondary nuclear reaction products, due to 9Be  +  p interaction, were observed with fast ion loss detectors, γ-ray spectrometers and neutron flux monitors and spectrometers. The possibility of using 9Be(p, d)2α and 9Be(p, α)6Li nuclear reactions to create a population of fast alpha particles and study their behaviour in non-active stage of ITER operation is discussed in the paper.

  14. Comparative Assessment of Gasification Based Coal Power Plants with Various CO2 Capture Technologies Producing Electricity and Hydrogen

    Science.gov (United States)

    2014-01-01

    Seven different types of gasification-based coal conversion processes for producing mainly electricity and in some cases hydrogen (H2), with and without carbon dioxide (CO2) capture, were compared on a consistent basis through simulation studies. The flowsheet for each process was developed in a chemical process simulation tool “Aspen Plus”. The pressure swing adsorption (PSA), physical absorption (Selexol), and chemical looping combustion (CLC) technologies were separately analyzed for processes with CO2 capture. The performances of the above three capture technologies were compared with respect to energetic and exergetic efficiencies, and the level of CO2 emission. The effect of air separation unit (ASU) and gas turbine (GT) integration on the power output of all the CO2 capture cases is assessed. Sensitivity analysis was carried out for the CLC process (electricity-only case) to examine the effect of temperature and water-cooling of the air reactor on the overall efficiency of the process. The results show that, when only electricity production in considered, the case using CLC technology has an electrical efficiency 1.3% and 2.3% higher than the PSA and Selexol based cases, respectively. The CLC based process achieves an overall CO2 capture efficiency of 99.9% in contrast to 89.9% for PSA and 93.5% for Selexol based processes. The overall efficiency of the CLC case for combined electricity and H2 production is marginally higher (by 0.3%) than Selexol and lower (by 0.6%) than PSA cases. The integration between the ASU and GT units benefits all three technologies in terms of electrical efficiency. Furthermore, our results suggest that it is favorable to operate the air reactor of the CLC process at higher temperatures with excess air supply in order to achieve higher power efficiency. PMID:24578590

  15. Japan`s New Sunshine Project. 20. 1995 annual summary of coal liquefaction and gasification

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-10-01

    The paper described a summary of the 1995 study on coal liquefaction and gasification under the New Sunshine Project. As for coal liquefaction, a study was made of liquefaction characteristics and catalysts of various coals. Also studied were liquefaction conditions for quality improvement of liquefaction products, an evaluation method of quality of coal liquid, and a utilization method of coal liquid. In order to prevent carbonization and realize effective liquefaction, a study was conducted for elucidation of the reaction mechanism of high pressure hydrogenation. In a 150t/d pilot plant using hydrogen transfer hydrogenation solvents, the NEDOL method was studied using various catalysts and kinds of coals. This is a step prior to data acquisition for engineering, actual construction of equipment and operation. A 1t/d process supporting unit is a unit to support it. The unit conducts studies on slurry letdown valves and synthetic iron sulfide catalysts, screening of Chinese coals, etc. As to coal gasification, the paper added to the basic research the combined cycle power generation using entrained flow coal gasification for improvement of thermal efficiency and environmental acceptability and the HYCOL method for hydrogen production. 68 refs., 40 figs.

  16. Hydrogen-deuterium exchange reaction of 2-methylpyridine catalyzed by several fatty acids

    International Nuclear Information System (INIS)

    Hirata, Hirohumi; Fukuzumi, Kazuo.

    1976-01-01

    Hydrogen-deuterium exchange reaction of 2-methylpyridine has been studied by using several fatty acids as catalysts. The reaction was carried out in a sealed pyrex tube at 120 0 C, and the contents of the products were determined by mass spectrometry. Reaction of 2-methylpyridine with monodeuteroacetic acid (1 : 1, mol/mol) arrived at a equilibrium (d 0 reversible d 1 reversible d 2 reversible d 3 ) in 2 hr (d 0 41%, d 1 42%, d 2 15%, d 3 2%). No exchange was observed for the reaction of pyridine with monodeuteroacetic acid. The conversion-time curves of typical series reactions (d 0 → d 1 → d 2 → d 3 ) were obtained for the fatty acid catalyzed exchange in deuterium oxide. The effect of the fatty acid RCO 2 H (substrate : fatty acid : D 2 O=1 : 0.86 : 27.6, mol/mol/mol) on the conversion was in the order of R; C 1 --C 3 4 --C 10 , where the reaction mixtures were homogeneous in the case of C 1 --C 3 and were heterogeneous in the case of C 4 --C 10 . The effects of the initial concentration of the substrates and the catalysts (RCO 2 H) on the total conversion were studied by using some fatty acids (R; C 2 , C 4 and C 9 ) in deuterium oxide (for 2 hr). The total conversion of the substrate increases with increasing the concentration of the acids. The total conversion decreases in the case of R=C 9 , but, increases in the case of R=C 2 with increasing the concentration of the substrate. In the case of reactions with low concentrations of the substrate, the reactivity was in the order of C 9 >C 4 >C 2 , while with high concentrations, the reactivity was in the order of C 4 >C 2 >C 9 and C 9 >C 4 >C 2 with high and low concentrations of the acids, respectively. A possible reaction mechanism was proposed and discussed. (auth.)

  17. Hydrogen production by water dissociation using ceramic membranes - annual report for FY 2010.

    Energy Technology Data Exchange (ETDEWEB)

    Balachandran, U.; Dorris, S. E.; Emerson, J. E.; Lee, T. H.; Lu, Y.; Park, C. Y.; Picciolo, J. J. (Energy Systems)

    2011-03-14

    The objective of this project is to develop dense ceramic membranes that can produce hydrogen via coal/coal gas-assisted water dissociation without using an external power supply or circuitry. This project grew from an effort to develop a dense ceramic membrane for separating hydrogen from gas mixtures such as those generated during coal gasification, methane partial oxidation, and water-gas shift reactions. That effort led to the development of various cermet (i.e., ceramic/metal composite) membranes that enable hydrogen production by two methods. In one method, a hydrogen transport membrane (HTM) selectively removes hydrogen from a gas mixture by transporting it through either a mixed protonic/electronic conductor or a hydrogen transport metal. In the other method, an oxygen transport membrane (OTM) generates hydrogen mixed with steam by removing oxygen that is generated through water splitting. This project focuses on the development of OTMs that efficiently produce hydrogen via the dissociation of water. Supercritical boilers offer very high-pressure steam that can be decomposed to provide pure hydrogen using OTMs. Oxygen resulting from the dissociation of steam can be used for coal gasification, enriched combustion, or synthesis gas production. Hydrogen and sequestration-ready CO{sub 2} can be produced from coal and steam by using the membrane being developed in this project. Although hydrogen can also be generated by high-temperature steam electrolysis, producing hydrogen by water splitting with a mixed-conducting membrane requires no electric power or electrical circuitry.

  18. Studies of reaction difference between γ-ray and glow discharge on hydrogenation of unsaturated fatty acid esters

    International Nuclear Information System (INIS)

    Sakoda, Tatsuya; Nieda, Hiroshi; Kitahara, Kazuta; Ando, Kiyomi

    2000-01-01

    Hydrogenation of unsaturated fatty acid esters using an inductively coupled plasma at low pressure was performed, and electron temperature and density were measured using a double-probe in order to investigate the reaction difference between γ-ray and glow discharge on hydrogenation. In this experiment, unsaturated fatty acid esters were partly hydrogenated by the hydrogen plasma that had electron temperature of 3.5 eV, which was more efficient than γ-ray irradiation method. As a result, it was found that the plasma can effectively supply electrons that had the optimum energy for hydrogenation at the interface of fatty acids as well as excited atoms and ions. Also, the plasma generated at low pressure would be possible to convert unsaturated fatty acids into saturated fatty acids without breaking the starting monomer. (author)

  19. Development of styrene divinyl benzene catalyst in isotopic exchange reaction of water and hydrogen

    International Nuclear Information System (INIS)

    Morishita, Teizo; Noda, Shigeyuki; Tan, Tsutomu; Noguchi, Hiroshi

    1982-01-01

    Styrene divinyl benzene copolymer (SDBC) is hydrophobic, and porous with large specific surface area. Utilizing these properties, the SDBC was used for the carrier of catalyst in water-hydrogen exchange reaction process, and the hydrophobic platinum catalyst with very high performance was able to be developed. However, the SDBC is usually fine particles smaller than 1 mm, and is not suitable as the filling catalyst for exchange reaction towers. Therefore, in this study, using only platinum as a catalyst metal, the improvement of the property of carriers was emphatically examined, and platinum bearing was proved with an optical or electron microscope. As the result, it was found that the SDBC catalyst showed high activity practically usable as the hydrophobic catalyst for heavy water or tritium exchange reaction. The characteristics of SDBC are explained. The manufacturing processes of the catalyst by making SDBC carriers with fine particles and letting them bear platinum are described. The results of the trial manufacture of spherical, extrusion-formed and honeycomb carrier catalysts are reported. Platinum must be dispersed over the large specific surface area of SDBC carriers. (Kako, I.)

  20. A study on the reaction of Zircaloy-4 tube with hydrogen/steam mixture

    Science.gov (United States)

    Lee, Ji-Min; Kook, Dong-Hak; Cho, Il-Je; Kim, Yong-Soo

    2017-08-01

    In order to fundamentally understand the secondary hydriding mechanism of zirconium alloy cladding, the reaction of commercial Zircaloy-4 tubes with hydrogen and steam mixture was studied using a thermo-gravimetric analyser with two variables, H2/H2O ratio and temperature. Phenomenological analysis revealed that in the steam starvation condition, i.e., when the H2/H2O ratio is greater than 104, hydriding is the dominant reaction and the weight gain increases linearly after a short incubation time. On the other hand, when the gas ratio is 5 × 102 or 103, both hydriding and oxidation reactions take place simultaneously, leading to three distinct regimes: primary hydriding, enhanced oxidation, and massive hydriding. Microstructural changes of oxide demonstrate that when the weight gain exceeds a certain critical value, massive hydriding takes place due to the significant localized crack development within the oxide, which possibly simulates the secondary hydriding failure in a defective fuel operation. This study reveals that the steam starvation condition above the critical H2/H2O ratio is only a necessary condition for the secondary hydriding failure and, as a sufficient condition, oxide needs to grow sufficiently to reach the critical thickness that produces substantial crack development. In other words, in a real defective fuel operation incident, the secondary failure is initiated only when both steam starvation and oxide degradation conditions are simultaneously met. Therefore, it is concluded that the indispensable time for the critical oxide growth primarily determines the triggering time of massive hydriding failure.

  1. Novel Zeolitic Imidazolate Framework/Polymer Membranes for Hydrogen Separations in Coal Processing

    Energy Technology Data Exchange (ETDEWEB)

    Musselman, Inga H.

    2013-01-31

    Nanoparticles of zeolitic imidazolate frameworks and other related hybrid materials were prepared by modifying published synthesis procedures by introducing bases, changing stoichiometric ratios, or adjusting reaction conditions. These materials were stable at temperatures >300 °C and were compatible with the polymer matrices used to prepare mixed-matrix membranes (MMMs). MMMs tested at 300 °C exhibited a >30 fold increase in permeability, compared to those measured at 35 °C, while maintaining H{sub 2}/CO{sub 2} selectivity. Measurements at high pressure (up to 30 atm) and high temperature (up to 300 °C) resulted in an increase in gas flux across the membrane with retention of selectivity. No variations in permeability were observed at high pressures at either 35 or 300 °C. CO{sub 2}-induced plasticization was not observed for Matrimid®, VTEC, and PBI polymers or their MMMs at 30 atm and 300 °C. Membrane surface modification by cross-linking with ethylenediamine resulted in an increase in H{sub 2}/CO{sub 2} selectivity at 35 °C. Spectrometric analysis showed that the cross-linking was effective to temperatures <150 °C. At higher temperatures, the cross-linked membranes exhibit a H2/CO2 selectivity similar to the uncrosslinked polymer.

  2. Hydrogen incorporation and radiation induced dynamics in metal-oxide-silicon structures. A study using nuclear reaction analysis

    International Nuclear Information System (INIS)

    Briere, M.A.

    1993-07-01

    Resonant nuclear reaction analysis, using the 1 H( 15 N, αγ) 12 C reaction at 6.4 MeV, has been successfully applied to the investigation of hydrogen incorporation and radiation induced migration in metal-oxide-silicon structures. A preliminary study of the influence of processing parameters on the H content of thermal oxides, with and without gate material present, has been performed. It is found that the dominant source of hydrogen in Al gate devices and dry oxides is often contamination, likely in the form of adsorbed water vapor, formed upon exposure to room air after removal from the oxidation furnace. Concentrations of hydrogen in the bulk oxide as high as 3 10 20 cm -3 (Al gate), and as low as 1 10 18 cm -3 (poly Si-gate) have been observed. Hydrogen accumulation at the Si-SiO 2 interface has been reproducibly demonstrated for as-oxidized samples, as well as for oxides exposed to H 2 containing atmospheres during subsequent thermal processing. The migration of hydrogen, from the bulk oxide to the silicon-oxide interface during NRA, has been observed and intensively investigated. A direct correlation between the hydrogen content of the bulk oxide and the radiation generated oxide charges and interface states is presented. These data provide strong support for the important role of hydrogen in determining the radiation sensitivity of electronic devices. (orig.)

  3. Medium temperature reaction between lanthanide and actinide carbides and hydrogen; Reaction a temperature moyenne entre les monocarbures de lanthanides et d'actinides et l'hydrogene

    Energy Technology Data Exchange (ETDEWEB)

    Dean, G; Lorenzelli, R; Pascard, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1964-07-01

    Hydrogen is fixed reversibly by the lanthanide and actinide mono carbides in the range 25 - 400 C, as for pure corresponding metals. Hydrogen goes into the carbides lattice through carbon vacancies and the total fixed amount is approximately equal to two hydrogen atoms per initial vacancy. Final products c.n thus be considered as carbo-hydrides of general formula M(C{sub 1-x}, H{sub 2x}). The primitive CFC, NaCl type, structure remains unchanged but expands strongly in the case of actinide carbides. With lanthanide carbides, hydrogenation induces a phase transformation with reappearance of the metal structure (HCP). Hydrogen decomposition pressures of all the studied carbo-hydrides are greater than those of the corresponding di-hydrides. (authors) [French] Les monocarbures d'actinides et de lanthanides fixent reversiblement de l'hydrogene a temperature peu elevee, a peu pres dans les memes conditions que les metaux purs correspondants. L'hydrogene penetre dans le reseau des carbures par l'intermediaire des lacunes de carbone, et la quantite totale fixee est approximativement egale a deux atomes d'hydrogene par lacune initiale. Les produits obtenus peuvent donc etre consideres comme des carbohydrures de formule generale M(C{sub 1-x}, H{sub 2x}). La structure d'origine CFC, type NaCl est conservee, mais avec une forte expansion, dans le cas des carbures d'actinides. En revanche, l'hydrogenation entraine un changement de phase cristalline avec retour a la structure du metal (HC) pour les carbures de lanthanides. Tous les carbohydrures etudies ont des tensions de decomposition en hydrogene superieures a celles des dihydrures correspondants. (auteurs)

  4. Monolithic Laser Scribed Graphene Scaffold with Atomic Layer Deposited Platinum for Hydrogen Evolution Reaction

    KAUST Repository

    Nayak, Pranati; Jiang, Qiu; Kurra, Narendra; Buttner, Ulrich; Wang, Xianbin; Alshareef, Husam N.

    2017-01-01

    The use of three-dimensional (3D) electrode architectures as scaffolds for conformal deposition of catalysts is an emerging research area with significant potential for electrocatalytic applications. In this study, we report the fabrication of monolithic, self-standing, 3D graphitic carbon scaffold with conformally deposited Pt by atomic layer deposition (ALD) as a hydrogen evolution reaction catalyst. Laser scribing is employed to transform polyimide into 3D porous graphitic carbon, which possesses good electronic conductivity and numerous edge plane sites. This laser scribed graphene (LSG) architecture makes it possible to fabricate monolithic electrocatalyst support without any binders or conductive additives. The synergistic effect between ALD of Pt on 3D network of LSG provides an avenue for minimal yet effective Pt usage, leading to an enhanced HER activity. This strategy establish a general approach for inexpensive and large scale HER device fabrication with minimum catalyst cost.

  5. 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

  6. General Tritium labelling of gentamicin C by catalytic hydrogen exchange reaction with tritiated water

    International Nuclear Information System (INIS)

    Suarez, C.; Diaz, D.

    1991-01-01

    Gentamicin C was labelled with tritium by means of a PtO 2 catalized hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H 2 O- 3 H, and 50 mg of prereduced PtO 2 ) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 o C, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accoumplished 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

  7. Editors' Choice Growth of Layered WS2Electrocatalysts for Highly Efficient Hydrogen Production Reaction

    KAUST Repository

    Alsabban, Merfat M.

    2016-08-18

    Seeking more economical alternative electrocatalysts without sacrificing much in performance to replace precious metal Pt is one of the major research topics in hydrogen evolution reactions (HER). Tungsten disulfide (WS2) has been recognized as a promising substitute for Pt owing to its high efficiency and low-cost. Since most existing works adopt solution-synthesized WS2 crystallites for HER, direct growth of WS2 layered materials on conducting substrates should offer new opportunities. The growth of WS2 by the thermolysis of ammonium tetrathiotungstate (NH4)(2)WS4 was examined under various gaseous environments. Structural analysis and electrochemical studies show that the H2S environment leads to the WS2 catalysts with superior HER performance with an extremely low overpotential (eta(10) = 184 mV). (C) The Author(s) 2016. Published by ECS. All rights reserved.

  8. Editors' Choice Growth of Layered WS2Electrocatalysts for Highly Efficient Hydrogen Production Reaction

    KAUST Repository

    Alsabban, Merfat M.; Min, Shixiong; Hedhili, Mohamed N.; Ming, Jun; Li, Lain-Jong; Huang, Kuo-Wei

    2016-01-01

    Seeking more economical alternative electrocatalysts without sacrificing much in performance to replace precious metal Pt is one of the major research topics in hydrogen evolution reactions (HER). Tungsten disulfide (WS2) has been recognized as a promising substitute for Pt owing to its high efficiency and low-cost. Since most existing works adopt solution-synthesized WS2 crystallites for HER, direct growth of WS2 layered materials on conducting substrates should offer new opportunities. The growth of WS2 by the thermolysis of ammonium tetrathiotungstate (NH4)(2)WS4 was examined under various gaseous environments. Structural analysis and electrochemical studies show that the H2S environment leads to the WS2 catalysts with superior HER performance with an extremely low overpotential (eta(10) = 184 mV). (C) The Author(s) 2016. Published by ECS. All rights reserved.

  9. Monolithic Laser Scribed Graphene Scaffold with Atomic Layer Deposited Platinum for Hydrogen Evolution Reaction

    KAUST Repository

    Nayak, Pranati

    2017-09-01

    The use of three-dimensional (3D) electrode architectures as scaffolds for conformal deposition of catalysts is an emerging research area with significant potential for electrocatalytic applications. In this study, we report the fabrication of monolithic, self-standing, 3D graphitic carbon scaffold with conformally deposited Pt by atomic layer deposition (ALD) as a hydrogen evolution reaction catalyst. Laser scribing is employed to transform polyimide into 3D porous graphitic carbon, which possesses good electronic conductivity and numerous edge plane sites. This laser scribed graphene (LSG) architecture makes it possible to fabricate monolithic electrocatalyst support without any binders or conductive additives. The synergistic effect between ALD of Pt on 3D network of LSG provides an avenue for minimal yet effective Pt usage, leading to an enhanced HER activity. This strategy establish a general approach for inexpensive and large scale HER device fabrication with minimum catalyst cost.

  10. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun; Zhang, Chenhui; Wang, Zhenyu; Zhu, Jian; Wen, Zhiwei; Zhao, Xingzhong; Zhang, Xixiang; Xu, Jun; Lu, Zhouguang

    2017-01-01

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  11. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun

    2017-12-27

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  12. Synthesis and structures of Al–Ti nanoparticles by hydrogen plasma-metal reaction

    International Nuclear Information System (INIS)

    Liu Tong; Zhang Tongwen; Zhu Mu; Qin Chenggong

    2012-01-01

    Three kinds of Al–Ti nanoparticles (7.7, 27.8, and 42.6 at.% Ti) have been prepared from Al–65, Al–85, and Al–88 at.% Ti master alloys by hydrogen plasma-metal reaction, with average particle sizes of 30, 25, and 80 nm, respectively. The higher evaporation rate of Al than Ti resulted in the low Ti contents in the nanoparticles than those in the master alloys. Microscopy observation revealed that the primary nanoparticles are spherical in shape, and occur as chain aggregates of several individual nanoparticles due to the faster collision rate than the coalescence rate. All the Al–Ti nanoparticles contain amorphous alumina layers of about 2–3 nm in thickness surrounding the crystalline core. AlTi intermetallic nanoparticles were successfully produced for Al–27.8 at.% Ti, with a single crystal of AlTi in one chain aggregate. The composite nanoparticles of Al together with some Al 3 Ti phases are prepared for Al–7.7 at.% Ti, with each phase in the individual particle of one chain aggregate. The composite nanoparticles of AlTi with some AlTi 3 were produced for Al–42.6 at.% Ti, with each phase in the individual particle of one chain aggregate. The formation mechanism of Al–Ti nanoparticles was interpreted in terms of phase transition and the effect of hydrogen.

  13. Dynamics of the reaction of the N+ ion with hydrogen isotopes and helium

    International Nuclear Information System (INIS)

    Ruska, W.E.W.

    1976-01-01

    Molecular beam techniques were used to study the reactive and non-reactive scattering of the nitrogen positive ion from hydrogen isotopes and helium, at energies above the stability limit for spectator stripping. Reactive scattering was observed from H 2 and HD targets. Non-reactive scattering was observed from H 2 and D 2 targets, and from He at one energy. A correlation diagram for the system is presented and compared with the available a priori calculations. Two surfaces are expected to lead to reaction. One is a 3 A 2 - 3 PI surface, the other, a 3 B 1 - 3 Σ - surface. Collinear approaches are expected to be most reactive on the 3 B 1 - 3 Σ - surface; noncollinear, on the 3 A 1 - 3 PI surface. Theoretical models are presented in which an incident hard sphere A, representing the projectile ion, strikes one of a pair of hard spheres B-C representing the B hydrogen molecule. After an impulsive A-B collision, an impulsive B-C collision may take place. The relative energy of A to B is then examined, and a reactive event is considered to have occurred if the energy is less than the dissociation energy for the A-B molecule. This model is treated both in the collinear case and in three dimensions. A graphical technique for the collinear case is summarized and applied to reaction on the 3 B 1 - 3 Σ - surface. An integral equation for the three-dimensional case is developed. A synthesis of two treatments, representing the behavior of the system on both reactive surfaces, and considering the charge-exchange channel, correctly predicts the observed product distribution. Predictions are also presented for the as yet unobserved case of reactive scattering from a D 2 target

  14. Electrodeposition of Nickel Nanoparticles for the Alkaline Hydrogen Evolution Reaction: Correlating Electrocatalytic Behavior and Chemical Composition.

    Science.gov (United States)

    Tao, Shasha; Yang, Florent; Schuch, Jona; Jaegermann, Wolfram; Kaiser, Bernhard

    2018-03-09

    Ni nanoparticles (NPs) consisting of Ni, NiO, and Ni(OH) 2 were formed on Ti substrates by electrodeposition as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. Additionally, the deposition parameters including the potential range and the scan rate were varied, and the resulting NPs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. The chemical composition of the NPs changed upon using different conditions, and it was found that the catalytic activity increased with an increase in the amount of NiO. From these data, optimized NPs were synthesized; the best sample showed an onset potential of approximately 0 V and an overpotential of 197 mV at a cathodic current density of 10 mA cm -2 as well as a small Tafel slope of 88 mV dec -1 in 1 m KOH, values that are comparable to those of Pt foil. These NPs consist of approximately 25 % Ni and Ni(OH) 2 each, as well as approximately 50 % NiO. This implies that to obtain a successful HER electrocatalyst, active sites with differing compositions have to be close to each other to promote the different reaction steps. Long-time measurements (30 h) showed almost complete transformation of the highly active catalyst compound consisting of Ni 0 , NiO, and Ni(OH) 2 into the less active Ni(OH) 2 phase. Nevertheless, the here-employed electrodeposition of nonprecious metal/metal-oxide combination compounds represents a promising alternative to Pt-based electrocatalysts for water reduction to hydrogen. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

    Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo5+ and S2 2- species in the MoSx, especially with S2 2- serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g-1 cm-2 h-1 (286 mmol g-1 cm-2 h-1) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

  16. Advances in interactive supported electro-catalysis for hydrogen and oxygen electrode reactions

    Energy Technology Data Exchange (ETDEWEB)

    Nedeljko V Krstajic; Ljiljana M Vracar; Jelena M Jaksic; Milan M Jaksic [Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia and Montenegro (Yugoslavia); Stelios G Neophytides; Miranda Labou; Jelena M Jaksic; Milan M Jaksic [Institute of Chemical Engineering and High Temperature Chemical Processes FORTH, and Department of Chemistry, University of Patras, 26500 Patras, (Greece); Reidar Tunold [University of Trondheim, NTNU, Institute of Industrial Electrochemistry, Trondheim, (Norway); Polycarpos Falaras [Institute of Physical Chemistry, NCSR Demokritos, Attikis, Athens, (Greece)

    2006-07-01

    Magneli phases have been introduced as an unique electron conductive and interactive support for electro-catalysis both in hydrogen (HELR) and oxygen (OELR) electrode reactions in water electrolysis and Low Temperature PEM Fuel Cells (LT PEM FC). The Strong Metal-Support Interaction (SMSI) that imposes the former implies: (i) the hypo-hyper-d inter-bonding effect and its catalytic consequences, and (ii) the interactive primary oxide (M-OH) spillover from the hypo-d-oxide support as a dynamic electrocatalytic contribution. The stronger the bonding, the more strained appear d-orbitals, thereby the less strong the intermediate adsorptive strength in the rate determining step (RDS), and consequently, the faster the facilitated catalytic electrode reaction arises. At the same time the primary oxide spillover transferred from the hypo-d-oxide support directly interferes and reacts either individually and directly to contribute to finish the oxygen reduction, or with other interactive species, like CO to contribute to the CO tolerance. In such a respect, the conditions to provide Au to act as the reversible hydrogen electrode have been proved either by its potentiodynamic surface reconstruction in a heavy water solution, or by the nano-structured SMSI Au on anatase titania with characteristic strained d-orbitals in such a hypo-hyper-d-interactive bonding (Au/TiO{sub 2}). In the same context, the monoatomic network dispersion of Pt upon Magneli phases makes it possible to produce an advanced interactive supported electro-catalyst for cathodic oxygen reduction (ORR). The strained hypo-hyper-d-inter-electronic and inter-d-orbital metal/hypo-d-oxide support bonding relative to the strength of the latter, has been inferred to be the basis of the synergistic electrocatalytic effect both in the HELR and ORR. (authors)

  17. Dechlorination of chloropicrin and 1,3-dichloropropene by hydrogen sulfide species: redox and nucleophilic substitution reactions.

    Science.gov (United States)

    Zheng, Wei; Yates, Scott R; Papiernik, Sharon K; Guo, Mingxin; Gan, Jianying

    2006-03-22

    The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.

  18. Japan`s New Sunshine Project. 1996 Annual Summary of Coal Liquefaction and Gasification; 1996 nendo new sunshine keikaku seika hokokusho gaiyoshu. Sekitan no ekika gasuka

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-11-01

    In reference to the results of the research and development under the fiscal 1996 New Sunshine Project, a report was summed up on coal liquefaction and coal gasification. As to the R and D of coal liquefaction technology, researches were conducted on liquefaction characteristics and engineering properties by coal kind, catalysts for coal liquefaction, liquefaction reaction of coal and reformation utilization of the liquefied products, liquefaction reaction mechanism and coking mechanism, solubility of coal in solvent and catalytic reaction mechanism, solvent reaction mechanism by hydrogen donor solvent, etc. Concerning the R and D of coal gasification technology, made were the basic study of eco-technology adaptable gasification technology and the study of coal gasification enhancing technology. Further, as to the development of bituminous coal liquefaction technology, carried out were the study in pilot plants and the support study of pilot plants. Additionally, R and D were done of the basic technology of coal liquefaction such as upgrading technology and environmentally acceptable coal liquefaction technology, and of coal hydrogasification technology. 3 refs., 81 figs., 25 tabs.

  19. The Synthesis and Electrocatalytic Activities of Molybdenum Sulfide for Hydrogen Evolution Reaction

    KAUST Repository

    Li, Zhengxing

    2014-07-01

    In the context of the future hydrogen economy, effective production of hydrogen (H2) from readily available and sustainable resources is of crucial importance. Hydrogen generation via water splitting by solar energy or electricity has attracted great attention in recent years. In comparison with photocatalytic water-splitting directly using solar light, which is ideal but the relevant technologies are not yet mature, electrolysis of water with catalyst is more practical at the current stage. The Pt-group noble metals are the most effective electrocatalysts for hydrogen evolution reaction (HER) from water, but their high costs limit their applications. Due to the earth-abundance and low price, MoS2 is expected to be a good alternative of the Pt-group metals for HER. Plenty of researches have been conducted for improving the HER activities of MoS2 by optimizing its synthesis method. However, it remains challenging to prepare MoS2 catalysts with high and controllable activity, and more investigations are still needed to better understand the structure-performance correlation in this system. In this thesis, we report a new strategy for fabricating MoS2 eletrocatalysts which gives rise to much improved HER performance and allows us to tune the electrocatalytic activity by varying the preparation conditions. Specifically, we sulfurized molybdenum oxide on the surface of a Ti foil electrode via a facile chemical vapor deposition (CVD) method, and directly used the electrode for HER testing. Depending on the CVD temperature, the MoO2-MoS2 nanocomposites show different HER activities. Under the optimal synthesis condition (400ºC), the resulting catalyst exhibited excellent HER activity: an onset potential (overpotential) of 0.095 V versus RHE and the Tafel slope of 40 mv/dec. Such a performance exceeds those of most reported MoS2 based HER electrocatalysts. We demonstrated that the CVD temperature has significant influence on the catalysts in crystallinity degree, particle

  20. Relationship Between Equilibrium Hydrogen Pressure and Exchange Current for the Hydrogen Electrode-Reaction at Mmni(3.9-X)Mn(0.4)A1(X)Co(0.7) Alloy Electrodes

    NARCIS (Netherlands)

    Senoh, H.; Morimoto, K.; Inoue, H.; Iwakura, C.; Notten, P.H.L.

    2000-01-01

    We present a theoretical relationship between equilibrium hydrogen pressure and exchange current for the hydrogen electrode reaction which considers the degree of hydrogen coverage at the electrode surface. Electrochemical measurements at MmNi3.9–xMn0.4AlxCo0.7 (0 x 0.8) electrodes were performed to

  1. Techno-economic assessment of hydrogen production from underground coal gasification (UCG) in Western Canada with carbon capture and sequestration (CCS) for upgrading bitumen from oil sands

    International Nuclear Information System (INIS)

    Olateju, Babatunde; Kumar, Amit

    2013-01-01

    Highlights: • Development of a techno-economic model for UCG-CCS and SMR-CCS. • Estimation of H 2 production costs with and without CCS for UCG and SMR. • UCG is more economical for H 2 production with CCS. • SMR is more cost efficient for H 2 production without CCS. • Cost competiveness is highly sensitive to the IRR differential between UCG and SMR. - Abstract: This paper examines the techno-economic viability of hydrogen production from underground coal gasification (UCG) in Western Canada, for the servicing of the oil sands bitumen upgrading industry. Hydrogen production for bitumen upgrading is predominantly achieved via steam methane reforming (SMR); which involves significant greenhouse gas (GHG) emissions along with considerable feedstock (natural gas) cost volatility. UCG is a formidable candidate for cost-competitive environmentally sustainable hydrogen production; given its negligible feedstock cost, the enormity of deep coal reserves in Western Canada and the favourable CO 2 sequestration characteristics of potential UCG sites in the Western Canadian sedimentary basin (WCSB). Techno-economic models were developed for UCG and SMR with and without CCS, to estimate the cost of hydrogen production including delivery to a bitumen upgrader. In this paper, at base case conditions, a 5% internal rate of return (IRR) differential between UCG and SMR was considered so as to account for the increased investment risk associated with UCG. The cost of UCG hydrogen production without CCS is estimated to be $1.78/kg of H 2 . With CCS, this increases to range of $2.11–$2.70/kg of H 2 , depending on the distance of the site for CO 2 sequestration from the UCG plant. The SMR hydrogen production cost without CCS is estimated to be $1.73/kg of H 2 . In similar fashion to UCG, this rises to a range of $2.14 to $2.41/kg of H 2 with the consideration of CCS. Lastly, for hydrogen production without CCS, UCG has a superior cost competitiveness in comparison to SMR

  2. The deuterium-exchange reaction between water and hydrogen with the thin-film hydrophobic catalyst

    International Nuclear Information System (INIS)

    Yamashita, Hisao; Mizumoto, Mamoru; Matsuda, Shimpei

    1985-01-01

    The deuterium-exchange reaction between water and hydrogen with a hydrophobic catalyst was studied. The hydrophobic catalyst was composed of platinum as an active component and porous poly(tetrafluoroethylene) (PTFE) as a support. The PTFE support was in two forms, i.e., (a) a pellet and (b) a thin-film with the thickness of 50 μm. The primary purpose of the thin film hydrophobic catalyst was to reduce the platinum usage in the reactor. The activity of the catalyst was measured in a trickle bed reactor at atmospheric pressure and temperature of 20 ∼ 70 deg C. It has been found that the employment of the thin-film catalyst reduced the platinum usage to 1/5 of the reactor in the case of using a conventional catalyst. Platinum particles on the thin-film catalyst work efficiently because the reactants were easily diffused to the active sites. It has also been found that the isotopic exchange rate with the thin-film catalyst increased with the increase in the ratio of liquid/gas and increased with the rise of the reaction temperature. It was found from an endurance test that the activity of the thin-film catalyst decreased gradually due to the condensation of water vapor in the catalyst, but was regenarated by heating the catalyst to remove the condensed water. (author)

  3. FY 1981 Report on the results of Sunshine Project. Coal energy; 1981 nendo sunshine keikaku seika hokokusho. Sekitan energy

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1981-07-01

    This report presents the results of (researches on solvolysis liquefaction mechanisms and reaction promotion with oil- and coal-based solvents), conducted as part of the research and development project for coal liquefaction techniques. The FY 1981 program includes researches on (1) the effects of liquefaction reaction conditions on liquefaction yield and production of light products for coal species of low degree of carbonization, including brown coal, (2) the effects of pretreatment of coal on its liquefaction reactivity, and (3) up-grading of the solvolysis coal liquid (SCL). For the item (1), HA240 (hydrogenated Ashland's A240) is used to investigate its liquefaction capacity for various coal species of low degree of carbonization, including brown coal. For the item (2), the effects of pretreatment in a hot water bath with reflux was investigated for sub-bituminous coal in the FY 1980. In the FY 1981, various pretreatment methods are attempted for enhancing liquefaction reactivity of brown coal. As a result, it is found that ash content of brown coal is decreased to one-third of the initial level, when it is treated in a diluted hydrochloric acid bath with reflux. For the item (3), SCL hydrogenated by Birch reduction (B-SCL, 1) is compared with H-SCL with respect to properties, structures and thermal crackability, to discuss the items required for the catalyst to be used in the second stage by clarifying effectiveness of the catalyst. (NEDO)

  4. Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

    Science.gov (United States)

    McCollom, Thomas M.; Donaldson, Christopher

    2016-06-01

    Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

  5. Report on the achievements in research and development of a coal liquefaction technology in the Sunshine Project in fiscal 1981. Development of a solvolysis liquefaction plant (research on realization of solvolysis pitch hydrogenation equipment); Sekitan ekika gijutsu no kenkyu kaihatsu, solvolysis ekika plant no kaihatsu seika hokokusho. Solvolysis pitch no suiten sochika kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1982-03-01

    Among researches on solvolysis coal liquefaction technologies in the Sunshine Project in fiscal 1981, this paper describes the research on realization of solvolysis pitch hydrogenation equipment. In realizing a hydrogenation and decomposition reacting equipment for the second stage reaction process, it is important to stabilize operation by preventing coking and catalytic deterioration in elevated temperature zones. Therefore, a reactor of catalytic fluid system was assumed. Fiscal 1981 has fabricated and experimented a flow testing equipment for the purpose of acquiring data for realization of the equipment. A reactor that can deal with temperatures higher than 400 degrees C was installed in a 0.1-t/d continuously operating equipment. For selecting adequate operating conditions, an operation manual was prepared from the results of the cold model test and the fundamental test on hydrogenation and decomposition. The devices used were verified to have good operability. As the gasification rate increases when the reaction temperature is raised, resulting in reduced oil yield, it is necessary to keep the temperature lower than 430 degrees C. Increased pressure does not increase the oil yield as much as it increases hydrogen consumption, hence pressure of 200 kg/cm{sup 2} or lower is suitable. The secondary hydrogenation solvent requires no proton donation performance, and light fraction should be preferable. Catalysts were also discussed, and a clue to improvements was obtained. (NEDO)

  6. Gasification of coal making use of nuclear processing heat

    International Nuclear Information System (INIS)

    Schilling, H.D.; Bonn, B.; Krauss, U.

    1981-01-01

    In the chapter 'Gasification of coal making use of nuclear processing heat', the steam gasification of brown coal and bituminous coal, the hydrogenating gasification of brown coal including nuclear process heat either by steam cracking methane in the steam reformer or by preheating the gasifying agent, as well as the hydrogenating gasification of bituminous coal are described. (HS) [de

  7. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.; Ravishankar, T.N.; Ramakrishnappa, T.; Nagaraju, Doddahalli H.; Krishna Pai, Ranjith

    2015-01-01

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic

  8. Cobalt-Embedded Nitrogen-Rich Carbon Nanotubes Efficiently Catalyze Hydrogen Evolution Reaction at All pH Values

    Czech Academy of Sciences Publication Activity Database

    Zou, X.; Huang, X.; Goswami, A.; Silva, R.; Sathe, B. R.; Mikmeková, Eliška; Asefa, T.

    2014-01-01

    Roč. 53, č. 17 (2014), s. 4372-4376 ISSN 1433-7851 R&D Projects: GA MŠk(CZ) LO1212 Institutional support: RVO:68081731 Keywords : carbon nanotubes * cobalt nanoparticles * electrocatalysis * hydrogen evolution reaction * water splitting Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 11.261, year: 2014

  9. The influence of reaction time on hydrogen sulphide removal from air by means of Fe(III)-EDTA/Fiban catalysts

    Science.gov (United States)

    Wasag, H.; Cel, W.; Chomczynska, M.; Kujawska, J.

    2018-05-01

    The paper deals with a new method of hydrogen sulphide removal from air by its filtration and selective catalytic oxidation with the use of fibrous carriers of Fe(III)-EDTA complex. The basis of these filtering materials includes fibrous ion exchangers with the complex immobilized on their functional groups. It has been established that the degree of catalytic hydrogen sulphide decomposition depends on the reaction time. Thus, the required degree of hydrogen sulphide removal from air could be easily controlled by applying appropriate thickness of the filtering layer under a given filtering velocity. It allows applying very thin filtering layers of the Fe(III)-EDTA/Fiban AK-22 or Fiban A-6 catalysts. The obtained results of the research confirm the applicability of these materials for deep air purification from hydrogen sulphide.

  10. Development of the work function approach to the underpotential deposition of metals. Application to the hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Trasatti, S.

    1975-01-01

    A theory is developed for the underpotential deposition of metals. Concepts are then extended to oxygen and hydrogen adsorption. Analysis of results shows that, unlike oxygen adsorption, hydrogen adsorption in solution probably follows a different pattern with respect to the gas phase situation. The hydrogen evolution reaction is discussed in the light of the above findings and it is shown that usual concepts regarding the reactivity scale of metals towards hydrogen should be reconsidered taking into account solvent and entropy effects. The latters can account for the behaviour of sp-metals. The formers are important with transition metals. The final picture is consistent with the idea that M-H 2 O interactions are much stronger on transition than on sp-metals. (orig.) [de

  11. Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

    Science.gov (United States)

    DeGregorio, Nicole; Iyengar, Srinivasan S

    2018-01-09

    We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

  12. Achievement report for fiscal 1981 on Sunshine Program. Basic research on solvent treatment technology for coal; 1981 nendo sekitan no yozai shori gijutsu no kiso kenkyu seika hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1982-03-01

    This research aims to prepare basic data on extraction liquefaction, which is one of the techniques of producing clean liquid fuels and chemical materials from coal, and thereby to contribute to the development of this process. The items taken up in this research are Item 1 on basic research using a small reactor, Item 2 on research on short-duration hydrogenation reaction in the intermediate temperature range, and Item 3 on basic research on the realization of a continuous operation. Item 1 is divided into Item (1) on primary hydrogenation extraction and Item (2) on secondary hydrogenation treatment. Under Item (1), hydrogenation characteristics are investigated of low rank coal with the Chinese brown coal heading the list and, under Item (2), the result of cleaner light oil production through secondary hydrogenation using different catalysts and the result of extraction from brown coal though secondary hydrogenation using a Co-Mo based catalyst are stated. Item 3 has been incorporated into Item 2 to stay there from this fiscal year on, and is divided into Item (1) on primary hydrogenation extraction and Item (2) on secondary hydrogenation treatment. Under Item (1), the result of a test operation of a small-size continuous coal hydrogenation extraction liquefaction unit using bituminous coal as specimen is reported and, under Item (2), the outline of a small-size fixed bed hydrogenation treatment unit newly installed this fiscal year is described. (NEDO)

  13. 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.

  14. The reaction of acid mine drainage with fly ash from coal combustion

    International Nuclear Information System (INIS)

    Kim, A.G.

    1999-01-01

    The placement of alkaline fly ash in abandoned, reclaimed or active surface coal mines is intended to reduce the amount of acid mine drainage (AMD) produced at such sites by neutralization, inhibition of acid forming bacteria, encapsulation of the pyrite or water diversion. A continuing concern with this application is the potential release of trace elements from the fly ash when it is placed in contact with AMD. To investigate the possible release of antimony, arsenic, barium, boron, cadmium, chromium, cobalt, copper, lead, nickel, selenium, and zinc from fly ash, a series of column leaching tests were conducted. A one kg fly ash sample, placed in a 5-cm by 1 m acrylic columns, was leached at a nominal rate of 250 mL/d for between 30 and 60 days. The leachant solutions were deionized water, and dilute solutions of sulfuric acid and ferric chloride. Leaching tests have been completed on 28 fly ash samples. leachate data, analyzed as the mass extracted with respect to the concentration in the solid, indicate that the release of trace elements is variable, with only barium and zinc extracted at greater than 50 pct of the amount present in the original sample. As a comparison, water quality changes have been monitored at three sites where fly ash grout was injected after reclamation to control AMD. When compared before and after grouting, small increases in pH and decreases in acidity at discharge points were observed. Concentrations of trace metals were found to be comparable in treated and untreated areas. When grouted and ungrouted areas were compared, the effect of the fly ash was shown to be localized in the areas of injection. These studies indicated that when fly ash is used as a reagent to control of AMD, the release of trace elements is relatively small

  15. Amorphous nickel/cobalt tungsten sulfide electrocatalysts for high-efficiency hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Lun [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Wu, Xinglong, E-mail: hkxlwu@nju.edu.cn [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Department of Physics, NingBo University, NingBo 315001 (China); Zhu, Xiaoshu [Center for Analysis and Testing, Nanjing Normal University, Nanjing 210093 (China); He, Chengyu; Meng, Ming; Gan, Zhixing [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Chu, Paul K. [Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China)

    2015-06-30

    Graphical abstract: - Highlights: • Amorphous nickel/cobalt tungsten sulfides were synthesized by a thermolytic process. • Amorphous NiWS and CoWS could realize hydrogen evolution efficiently. • Ni/Co promotion and annealing alter the porous structure and chemical bonding states. • Active sites on the surface of amorphous WS{sub x} are increased with Ni or Co doping. • Amorphous NiWS and CoWS have immense potentials in water splitting devices. - Abstract: The hydrogen evolution reaction (HER), an appealing solution for future energy supply, requires efficient and inexpensive electrocatalysts with abundant active surface sites. Although crystalline MoS{sub 2} and WS{sub 2} are promising candidates, their activity is dominated by edge sites. Amorphous tungsten sulfide prepared so far lacks the required active sites and its application has thus been hampered. In this work, nickel and cobalt incorporated amorphous tungsten sulfide synthesized by a thermolytic process is demonstrated to enhance the HER efficiency dramatically. The amorphous nickel tungsten sulfide (amorphous NiWS) annealed at 210 °C delivers the best HER performance in this system boasting a Tafel slope of 55 mV per decade and current density of 8.6 mA cm{sup −2} at 250 mV overpotential in a sustained test for 24 h. The introduction of Ni or Co into the catalyst and subsequent thermal treatment alters the porous structure and chemical bonding states thereby increasing the density of active sites on the surface.

  16. Co-pyrolysis of coal with hydrogen-rich gases. 1. Coal pyrolysis under coke-oven gas and synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Liao, H.; Li, B.; Zhang, B. [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion

    1998-06-01

    To improve the economics of the hydropyrolysis process, it has been suggested that cheaper hydrogen-rich gases (such as coke oven gas, synthesis gas) could be used instead of pure hydrogen. Pyrolysis of Chinese Xianfeng lignite was carried out with coke oven gas (COG) and synthesis gas (SG) as reactive gases at 0.1-5 MPa and at a final temperature up to 650{degree}C with a heating rate of 5-25{degree}C min{sup -1} in a 10 g fixed-bed reactor. The results indicate that it is possible to use COG and SG instead of pure hydrogen in hydropyrolysis, but that the experimental conditions must be adjusted to optimize the yields of the valuable chemicals. 14 refs., 3 figs., 6 tabs.

  17. Effect of intermolecular cohesion on coal liquefaction. 3. Reactivity of oxygen methylated coal; Sekitan teibunshika hanno ni okeru bunshikan gyoshuryoku no koka. 3. O-methyl ka tan no hanno tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Sasaki, M.; Nagaishi, H.; Yoshida, T. [Hokkaido National Industrial Research Institute, Sapporo (Japan)

    1996-10-28

    The reactivity of oxygen methylated coal was studied to control hydrogen bond in bituminous coal liquefaction and intermolecular cohesion such as van der Waals force. In experiment, crushed and dried Illinois coal of 100mesh or less was used as specimen, and oxygen methylated coal was prepared by Liotta`s method using tetrabutylammonium halide. Coal liquefaction was conducted in an electromagnetic agitation autoclave using tetralin solvent under initial hydrogen pressure of 100kg/cm{sup 2} while heating. The molecular weight distribution of the products obtained was measured by gel permeation chromatography (GPC) analysis. The experimental results are as follows. The effect of intermolecular cohesion in bituminous coal on the reactivity is mainly derived from decomposing reaction from preasphaltene to oil. Yields of oil fraction by methylation increase corresponding to release of intermolecular cohesion. Since the thermal release is promoted with temperature rise, the difference in yield due to different treatments decreases. 5 refs., 3 figs., 1 tab.

  18. Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

    2018-05-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

  19. Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

    Science.gov (United States)

    Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

    2014-12-25

    Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

  20. Dynamics of the reaction of the N/sup +/ ion with hydrogen isotopes and helium

    Energy Technology Data Exchange (ETDEWEB)

    Ruska, W.E.W.

    1976-06-28

    Molecular beam techniques were used to study the reactive and non-reactive scattering of the nitrogen positive ion from hydrogen isotopes and helium, at energies above the stability limit for spectator stripping. Reactive scattering was observed from H/sub 2/ and HD targets. Non-reactive scattering was observed from H/sub 2/ and D/sub 2/ targets, and from He at one energy. A correlation diagram for the system is presented and compared with the available a priori calculations. Two surfaces are expected to lead to reaction. One is a /sup 3/A/sub 2/ - /sup 3/PI surface, the other, a /sup 3/B/sub 1/ - /sup 3/..sigma../sup -/ surface. Collinear approaches are expected to be most reactive on the /sup 3/B/sub 1/ - /sup 3/..sigma../sup -/ surface; noncollinear, on the /sup 3/A/sub 1/ - /sup 3/PI surface. Theoretical models are presented in which an incident hard sphere A, representing the projectile ion, strikes one of a pair of hard spheres B-C representing the B hydrogen molecule. After an impulsive A-B collision, an impulsive B-C collision may take place. The relative energy of A to B is then examined, and a reactive event is considered to have occurred if the energy is less than the dissociation energy for the A-B molecule. This model is treated both in the collinear case and in three dimensions. A graphical technique for the collinear case is summarized and applied to reaction on the /sup 3/B/sub 1/ - /sup 3/..sigma../sup -/ surface. An integral equation for the three-dimensional case is developed. A synthesis of two treatments, representing the behavior of the system on both reactive surfaces, and considering the charge-exchange channel, correctly predicts the observed product distribution. Predictions are also presented for the as yet unobserved case of reactive scattering from a D/sub 2/ target.

  1. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

    Science.gov (United States)

    Mahmood, Javeed; Li, Feng; Jung, Sun-Min; Okyay, Mahmut Sait; Ahmad, Ishfaq; Kim, Seok-Jin; Park, Noejung; Jeong, Hu Young; Baek, Jong-Beom

    2017-05-01

    The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (˜65 kcal mol-1), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s-1 in 0.5 M H2SO4 solution; 0.75 H2 s-1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm-2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

  2. Ultrafine Iridium Oxide Nanorods Synthesized by Molten Salt Method toward Electrocatalytic Oxygen and Hydrogen Evolution Reactions

    International Nuclear Information System (INIS)

    Ahmed, Jahangeer; Mao, Yuanbing

    2016-01-01

    Highlights: • Ultrafine iridium oxide nanorods were synthesized by a molten salt method at 650 °C. • They show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions. • These results are comparable with, and in most cases, higher than reported data in the literature. • This study reports a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure. • These IrO_2 NRs are expected to serve as a benchmark to develop active electrocatalysts. - Abstract: Ultrafine iridium oxide nanorods (IrO_2 NRs) were successfully synthesized using a molten salt method at 650 °C. The structural and morphological characterizations of these IrO_2 NRs were carried out by powder X-ray diffraction, Raman spectroscopy and electron microscopic techniques. Compared to commercial IrO_2 nanoparticles (IrO_2 NPs) and previous reports, these IrO_2 NRs show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions by passing either N_2 or O_2 gas in a 0.5 M KOH electrolyte before electrochemical measurements, including cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Specifically, the current densities from the as-synthesized IrO_2 NRs and commercial IrO_2 NPs were measured in 0.5 M KOH electrolyte to be 70 and 58 (OER, deaerated, at 0.6 V versus Ag/AgCl), 71 and 61 (OER, O_2, from −0.10 to 1.0 V versus Ag/AgCl at 50 mV/s), and 25 and 14 (HER, deaerated, at −1.4 V versus Ag/AgCl) mA/cm"2, respectively. These results are comparable with, and in most cases, higher than reported data in the literature. Therefore, the current study reports not only a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure, and it is expected that these IrO_2 NRs can serve as a benchmark in the development of active OER and HER (photo)electrocatalysts for various applications.

  3. Phenomena and significance of intermediate spillover in electrocatalysis of oxygen and hydrogen electrode reactions

    Directory of Open Access Journals (Sweden)

    Jakšić Jelena M.

    2012-01-01

    Full Text Available Altervalent hypo-d-oxides of transition metal series impose spontaneous dissociative adsorption of water molecules and pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/HxWO3 under cathodic, and/or its hydrated state (Pt/W(OH6 responsible for the primary oxide (Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H0.35WO3 Pt/W(OH6, and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. As the consequence, the new striking and unpredictable prospects both in law and medium temperature proton exchange membrane fuell cell (L&MT PEMFC and water electrolysis (WE have been opened by the interactive supported individual (Pt, Pd, Ni or prevailing hyper-d-electronic nanostructured intermetallic phase clusters (WPt3, NbPt3, HfPd3, ZrNi3, grafted upon and within high altervalent capacity hypo-d-oxides (WO3, Nb2O5, Ta2O5, TiO2 and their proper mixed valence compounds, to create a novel type of alterpolar interchangeable composite electrocatalysts for hydrogen and oxygen electrode reactions. Whereas in aqueous media Pt (Pt/C features either chemisorbed catalytic surface properties of H-adatoms (Pt-H, or surface oxide (Pt=O, missing any effusion of other interacting species, new generation and selection of composite and interactive strong metal-support interaction (SMSI electrocatalysts in condensed wet state primarily characterizes interchangeable extremely fast reversible spillover of either H-adatoms, or the primary oxides (Pt-OH, Au-OH, or the invertible bronze type behavior of these significant interactive electrocatalytic ingredients. Such nanostructured type electrocatalysts, even of mixed hypo-d-oxide structure (Pt/H0.35WO3/TiO2/C, Pt/HxNbO3/TiO2/C, have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron

  4. Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers.

    Science.gov (United States)

    Reva, Igor; Nowak, Maciej J; Lapinski, Leszek; Fausto, Rui

    2015-02-21

    Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in isolated thiophenol molecules. Upon irradiation at 290-285 nm, the initial thiol form of thiophenol converted into its thione isomer, cyclohexa-2,4-diene-1-thione. This conversion occurs by transfer of an H atom from the SH group to a carbon atom at the ortho position of the ring. Subsequent irradiation at longer wavelengths (300-427 nm) demonstrated that this UV-induced hydrogen-atom transfer is photoreversible. Moreover, upon irradiation at 400-425 nm, the cyclohexa-2,4-diene-1-thione product converts, by transfer of a hydrogen atom from the ortho to para position, into another thione isomer, cyclohexa-2,5-diene-1-thione. The latter thione isomer is also photoreactive and is consumed if irradiated at λ atom-transfer isomerization reactions dominate the unimolecular photochemistry of thiophenol confined in a solid argon matrix. A set of low-intensity infrared bands, observed in the spectra of UV irradiated thiophenol, indicates the presence of a phenylthiyl radical with an H- atom detached from the SH group. Alongside the H-atom-transfer and H-atom-detachment processes, the ring-opening photoreaction occurred in cyclohexa-2,4-diene-1-thione by the cleavage of the C-C bond at the alpha position with respect to the thiocarbonyl C[double bond, length as m-dash]S group. The resulting open-ring conjugated thioketene adopts several isomeric forms, differing by orientations around single and double bonds. The species photogenerated upon UV irradiation of thiophenol were identified by comparison of their experimental infrared spectra with the spectra theoretically calculated for

  5. Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical.

    Science.gov (United States)

    Parab, Prajakta Rajaram; Heufer, K Alexander; Fernandes, Ravi Xavier

    2018-04-25

    Isopentanol is a potential next-generation biofuel for future applications to Homogeneous Charge Compression Ignition (HCCI) engine concepts. To provide insights into the combustion behavior of isopentanol, especially to its auto-ignition behavior which is linked both to efficiency and pollutant formation in real combustion systems, detailed quantum chemical studies for crucial reactions are desired. H-Abstraction reaction rates from fuel molecules are key initiation steps for chain branching required for auto-ignition. In this study, rate constants are determined for the hydrogen atom abstraction reactions from isopentanol by the H atom and HO2˙ radical by implementing the CBS-QB3 composite method. For the treatment of the internal rotors, a Pitzer-Gwinn-like approximation is applied. On comparing the computed reaction energies, the highest exothermicity (ΔE = -46 kJ mol-1) is depicted for Hα abstraction by the H atom whereas the lowest endothermicity (ΔE = 29 kJ mol-1) is shown for the abstraction of Hα by the HO2˙ radical. The formation of hydrogen bonding is found to affect the kinetics of the H atom abstraction reactions by the HO2˙ radical. Further above 750 K, the calculated high pressure limit rate constants indicate that the total contribution from delta carbon sites (Cδ) is predominant for hydrogen atom abstraction by the H atom and HO2˙ radical.

  6. Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural.

    Science.gov (United States)

    Brentzel, Zachary J; Barnett, Kevin J; Huang, Kefeng; Maravelias, Christos T; Dumesic, James A; Huber, George W

    2017-04-10

    A process for the synthesis of 1,5-pentanediol (1,5-PD) with 84 % yield from furfural is developed, utilizing dehydration/hydration, ring-opening tautomerization, and hydrogenation reactions. Although this process has more reaction steps than the traditional direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA), techno-economic analyses demonstrate that this process is the economically preferred route for the synthesis of biorenewable 1,5-PD. 2-Hydroxytetrahydropyran (2-HY-THP) is the key reaction pathway intermediate that allows for a decrease in the minimum selling price of 1,5-PD. The reactivity of 2-HY-THP is 80 times greater than that of THFA over a bimetallic hydrogenolysis catalyst. This enhanced reactivity is a result of the ring-opening tautomerization to 5-hydoxyvaleraldehyde and subsequent hydrogenation to 1,5-PD. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Use of nuclear reactions and ion channeling techniques for depth profiling hydrogen isotopes in solids

    International Nuclear Information System (INIS)

    Appleton, B.R.

    1979-01-01

    Hydrogen has always played a preeminent role in materials science because it so readily alters the physical and chemical properties of materials. However, it is often difficult to determine its role because it is one of the most elusive constituents to detect. More recently hydrogen detection has become necessary in numerous energy-related fields. In fusion energy one must understand plasma particle (hydrogen isotope) recycling, trapping and reemission, as well as the effects of hydrogen on the materials properties of first wall structures in plasma devices (i.e., hydrogen embrittlement, sputtering, blistering, etc.). In geology the presence of hydrogen in various forms alters the mechanical properties of many minerals in the earth's crust and enters directly into studies of tectonic processes. Evaluation of hydrogen in moon rocks increases our understanding of solar wind activity. In solar energy, hydrogen plays an important role in amorphous silicon used in fabricating solar cells. Detection of hydrogen is clearly important in the fossil fuel area. Many of the conventional elemental analysis techniques are not directly applicable to hydrogen determination and others can only detect hydrogen when it is in combination with other elements (i.e., H 2 O, OH, etc.). In this paper we discuss the use of ion beam techniques for obtaining quantitative depth information on hydrogen in materials and discuss the application of these techniques to several problems important in some of the areas mentioned

  8. SiC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION; F

    International Nuclear Information System (INIS)

    Paul K.T. Liu

    2001-01-01

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

  9. Redox reactions induced by hydrogen in deep geological nuclear waste disposal

    International Nuclear Information System (INIS)

    Truche, L.

    2009-10-01

    The aim of this study is to evaluate the abiotic hydrogen reactivity in deep geological nuclear waste storage. One crucial research interest concerns the role of H 2 as a reducing agent for the aqueous/mineral oxidised species present in the site. Preliminary batch experiments carried out with Callovo-Oxfordian argillite, synthetic pore water and H 2 gas lead to an important H 2 S production, in only few hours at 250 C to few months at 90 C. In order to explore whether H 2 S can originate from sulphate or pyrite (few percents of the argillite) reduction we performed dedicated experiments. Sulphate reduction experimented in di-phasic systems (water+gas) at 250-300 C and under 4 to 16 bar H 2 partial pressure exhibits a high activation energy (131 kJ/mol) and requires H 2 S initiation and low pH condition as already observed in other published TSR experiments. The corresponding half-life is 210,000 yr at 90 C (thermal peak of the site). On the contrary, pyrite reduction into pyrrhotite by H 2 occurs in few days at temperature as low as 90 C at pH buffered by calcite. The rate of the reaction could be described by a diffusion-like rate law in the 90-180 C temperature interval. The obtained results suggest that pyrite reduction is a process controlled both by the H 2 diffusion across the pyrrhotite pits increasing during reaction progress and the reductive dissolution of pyrite. These new kinetics data can be applied in computation modelling, to evaluate the degree and extent of gas pressure buildup by taking into account the H 2 reactive geochemistry. (author)

  10. Effect of addition of water-soluble salts on the hydrogen generation of aluminum in reaction with hot water

    International Nuclear Information System (INIS)

    Razavi-Tousi, S.S.; Szpunar, J.A.

    2016-01-01

    Aluminum powder was ball milled for different durations of time with different weight percentages of water-soluble salts (NaCl and KCl). The hydrogen generation of each mixture in reaction with hot water was measured. A scanning electron microscope (SEM) as well as energy-dispersive spectroscopy (EDS) were used to investigate the morphology, surfaces and cross sections of the produced particles. The results show that the presence of salts in the microstructure of the aluminum considerably increases the hydrogen generation rate. At shorter milling times, the salt covers the aluminum particles and becomes embedded in layers within the aluminum matrix. At higher milling durations, salt and aluminum phases form composite particles. A higher percentage of the second phase significantly decreases the milling time needed for activation of the aluminum particles. Based on the EDS results from cross sections of the milled particles, a mechanism for improvement of the hydrogen generation rate in the presence of salts is suggested. - Highlights: • Milling and water soluble salts have a synergic effect on hydrogen generation. • Salt and aluminum form composite particles by milling. • Salt is dissolved in water leaving aluminum with much fresh surfaces for the reaction. • The chemical effect of salt on the reaction is negligible compared to its structural effect.

  11. Synthesis of monoclinic Celsian from Coal Fly Ash by using a one-step solid-state reaction process

    Energy Technology Data Exchange (ETDEWEB)

    Long-Gonzalez, D.; Lopez-Cuevas, J.; Gutierrez-Chavarria, C.A.; Pena, P.; Baudin, C.; Turrillas, X. [CINVESTAV, Coahuila (Mexico)

    2010-03-15

    Monoclinic (Celsian) and hexagonal (Hexacelsian) Ba1-xSrxAl{sub 2}Si2O8 solid solutions, where x=0, 0.25, 0.375, 0.5, 0.75 or 1, were synthesized by using Coal Fly Ash (CFA) as main raw material, employing a simple one-step solid-state reaction process involving thermal treatment for 5 h at 850-1300{sup o}C. Fully monoclinic Celsian was obtained at 1200{sup o} C/5 h, for SrO contents of 0.25 {<=} x {<=} 0.75. However, an optimum SrO level of 0.25 {<=} x {<=} 0.375 was recommended for the stabilization of Celsian. These synthesis conditions represent a significant improvement over the higher temperatures, longer times and/or multi-step processes needed to obtain fully monoclinic Celsian, when other raw materials are used for this purpose, according to previous literature. These results were attributed to the role of the chemical and phase constitution of CFA as well as to a likely mineralizing effect of CaO and TiO{sub 2} present in it, which enhanced the Hexacelsian to Celsian conversion.

  12. Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

    Science.gov (United States)

    Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

    2018-05-22

    Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

  13. Symmetrical synergy of hybrid Co9S8-MoSx electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng

    2017-01-07

    There exists a strong demand to replace expensive noble metal catalysts with efficient and earth-abundant catalysts for hydrogen evolution reaction (HER). Recently the Co- and Mo-based sulfides such as CoS2, Co9S8, and MoSx have been considered as several promising HER candidates. Here, a highly active and stable hybrid electrocatalyst 3D flower-like hierarchical Co9S8 nanosheets incorporated with MoSx has been developed via a one-step sulfurization method. Since the amounts of Co9S8 and MoSx are easily adjustable, we verify that small amounts of MoSx promotes the HER activity of Co9S8, and vise versa. In other words, we validate that symmetric synergy for HER in the Co- and Mo-based sulfide hybrid catalysts, a long-standing question requiring clear experimental proofs. Meanwhile, the best electrocatalyst Co9S8-30@MoSx/CC in this study exhibits excellent HER performance with an overpotential of −98 mV at −10 mA/cm2, a small Tafel slope of 64.8 mV/dec, and prominent electrochemical stability.

  14. Boron-dependency of molybdenum boride electrocatalysts for the hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyounmyung; Encinas, Andrew; Fokwa, Boniface P.T. [Department of Chemistry, University of California, Riverside, CA (United States); Department of Chemical and Environmental Engineering, University of California, Riverside, CA (United States); Scheifers, Jan P.; Zhang, Yuemei [Department of Chemistry, University of California, Riverside, CA (United States)

    2017-05-08

    Molybdenum-based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo{sub 2}B, α-MoB, β-MoB, and MoB{sub 2} by arc-melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X-ray photoelectron spectroscopy (XPS) for the first time; MoB{sub 2} and β-MoB show excellent activity in the same range as the recently reported α-MoB and β-Mo{sub 2}C phases, while the molybdenum richest phase Mo{sub 2}B show significantly lower HER activity, indicating a strong boron-dependency of these borides for the HER. In addition, MoB{sub 2} and β-MoB show long-term cycle stability in acidic solution. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Synthesis of Fe-Al nanoparticles by hydrogen plasma-metal reaction

    CERN Document Server

    Liu Tong; Li Xing Guo

    2003-01-01

    Fe-Al nanoparticles of eight kinds have been prepared by hydrogen plasma-metal reaction. The morphology, crystal structure, and chemical composition of the nanoparticles obtained were investigated by transmission electron microscopy (TEM), x-ray diffractometry (XRD), and induction-coupled plasma spectroscopy. The particle size was determined by TEM and Brunaumer-Emmet-Teller gas adsorption. It was found that all the nanoparticles have spherical shapes, with average particle size in the range of 29-46 nm. The oxide layer in nanoparticles containing Al after passivation is not observable by XRD and TEM. The Al contents in Fe-Al ultrafine particles are about 1.2-1.5 times those in the master alloys. The evaporation speeds of Al and Fe in Fe-Al alloys are mutually accelerated at a certain composition. The crystal structures of the Fe-Al nanoparticles vary with the composition of the master alloys. Pure Fe sub 3 Al (D0 sub 3) and FeAl (B2) structures are successfully produced with 15 and 25 at.% Al in bulks, respe...

  16. Symmetrical synergy of hybrid CoS2-WS2 electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng; Yang, Xiulin; Li, Henan; Hedhili, Mohamed N.; Huang, Kuo-Wei; Li, Lain-Jong; Zhang, Wenjing

    2017-01-01

    A highly active and stable hybrid electrocatalyst 3D hierarchical CoS2 nanosheets incorporated with WS2 (CoS2@WS2) has been developed via a one-step sulfurization method for the first time, where the contents of WS2 can be adjusted easily. We first prove the addition of small amounts of WS2 enhances the hydrogen evolution reaction (HER) performance of CoS2, and vise versa. In other words, we validated the symmetric synergy for HER between the Co- and W-based sulfide hybrid catalysts. In addition, we confirmed that the formation of nanointerfaces of Co-S-W between CoS2 and WS2 was responsible for the excellent HER activity (an overpotential of -97.2 mV at -10 mA/cm2, a small Tafel slope of 66.0 mV/dec, and prominent electrochemical stability) of hybrid electrocatalyst CoS2@WS2.

  17. WS{sub 2} nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Han, Guan-Qun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Yan-Ru; Hu, Wen-Hui [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2015-11-01

    WS{sub 2} nanosheets (WS{sub 2} NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS{sub 2} (E-WS{sub 2}). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS{sub 2} consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS{sub 2}, with a low overpotential of 80 mV and high current density (10 mA cm{sup −2}, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS{sub 2} for HER. • E-WS{sub 2} shows the better electrocatalytic activity than bulk WS{sub 2}. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

  18. Dealloyed Pt3Co nanoparticles with higher geometric strain for superior hydrogen evolution reaction

    Science.gov (United States)

    Saquib, Mohammad; Halder, Aditi

    2018-06-01

    In the present work, the effect of surface strain in the carbon supported Pt3Co dealloy catalyst towards hydrogen evolution reaction (HER) has been reported. Dealloying process is adopted to generate the geometric strain in Pt3Co/C alloy by preferential dissolution of non-noble metal (Co) from the alloy. The developed geometric strain has been estimated by different microstructural characterization techniques. Electrochemical studies showed that the highest current density for HER was obtained for Pt3Co/C dealloy catalyst and it was nearly 2 and 5 times higher than Pt3Co/C alloy and Pt/C respectively. Tafel slope for HER was improved from 49 (Pt/C) to 34 mV dec-1 (Pt3Co/C dealloy), indicating that the surface strain plays important role in the improvement of the catalytic activity of Pt3Co catalyst. The chronoamperometry data, LSV curves and ECSA values before and after chronoamperometry confirmed that Pt3Co/C dealloy catalyst was a stable as well as a durable electrocatalyst for HER.

  19. Electrolytic Synthesis of Ni-W-MWCNT Composite Coating for Alkaline Hydrogen Evolution Reaction

    Science.gov (United States)

    Elias, Liju; Hegde, A. Chitharanjan

    2018-03-01

    Nickel-tungsten multi-walled carbon nanotube (Ni-W-MWCNT) composite films were fabricated by an electrodeposition technique, and their electrocatalytic activity toward hydrogen evolution reaction (HER) was studied. Ni-W-MWCNT composite films with a homogeneous dispersion of MWCNTs were deposited from an optimal Ni-W plating bath containing functionalized MWCNTs, under galvanostatic condition. The presence of functionalized MWCNT was found to enhance the induced codeposition of the reluctant metal W and resulted in a W-rich composite coating with improved properties. The electrocatalytic behaviors of Ni-W-MWCNT composite coating toward HER were studied by cyclic voltammetry (CV) and chronopotentiometry techniques in 1.0 M KOH medium. Further, Tafel polarization and electrochemical impedance spectroscopy (EIS) studies were carried out to establish the kinetics of HER on the alloy and composite electrodes. The experimental results revealed that the addition of MWCNTs (having a diameter of around 10-15 nm) into the alloy plating bath has a significant effect on the electrocatalytic behavior of Ni-W alloy deposit. The Ni-W-MWCNT composite coating was found to show better HER activity than the conventional Ni-W alloy coating. The enhanced electrocatalytic activity of Ni-W-MWCNT composite coating is attributed to the MWCNT intersticed in the deposit matrix, evidenced by surface morphology, composition and phase structure of the coating through SEM, EDS and XRD analyses, respectively.

  20. Ruthenium/Graphene-like Layered Carbon Composite as an Efficient Hydrogen Evolution Reaction Electrocatalyst.

    Science.gov (United States)

    Chen, Zhe; Lu, Jinfeng; Ai, Yuejie; Ji, Yongfei; Adschiri, Tadafumi; Wan, Lijun

    2016-12-28

    Efficient water splitting through electrocatalysis has been studied extensively in modern energy devices, while the development of catalysts with activity and stability comparable to those of Pt is still a great challenge. In this work, we successfully developed a facile route to synthesize graphene-like layered carbon (GLC) from a layered silicate template. The obtained GLC has layered structure similar to that of the template and can be used as support to load ultrasmall Ru nanoparticles on it in supercritical water. The specific structure and surface properties of GLC enable Ru nanoparticles to disperse highly uniformly on it even at a large loading amount (62 wt %). When the novel Ru/GLC was used as catalyst on a glass carbon electrode for hydrogen evolution reaction (HER) in a 0.5 M H 2 SO 4 solution, it exhibits an extremely low onset potential of only 3 mV and a small Tafel slope of 46 mV/decade. The outstanding performance proved that Ru/GLC is highly active catalyst for HER, comparable with transition-metal dichalcogenides or selenides. As the price of ruthenium is much lower than platinum, our study shows that Ru/GLC might be a promising candidate as an HER catalyst in future energy applications.

  1. High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Towards Hydrogen Evolution Reaction

    KAUST Repository

    Coy, Emerson

    2017-08-22

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced price and similar catalytic properties. However, most of the studied structures to date neglect long lasting chemical and structural stability, focusing only on electrochemical efficiency. Herein we report on a new approach to easily deposit and control the micro/nanostructure of thin film electrodes based on niobium carbide (NbC) and their electrocatalytic response. We will show that, by improving the mechanical properties of the NbC electrodes, microstructure and mechanical resilience can be obtained whilst maintaining high electro catalytic response. We also address the influence of other parameters such as conductivity and chemical composition on the overall performance of the thin film electrodes. Finally, we show that nanocomposite NbC electrodes are promising candidates towards HER , and furthermore, that the methodology presented here is suitable to produce other transition metal carbides (TM-C) with improved catalytic and mechanical properties.

  2. 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.

  3. WS_2 nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Han, Guan-Qun; Liu, Yan-Ru; Hu, Wen-Hui; Dong, Bin; Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi; Liu, Chen-Guang

    2015-01-01

    WS_2 nanosheets (WS_2 NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS_2 (E-WS_2). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS_2 consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS_2, with a low overpotential of 80 mV and high current density (10 mA cm"−"2, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS_2 for HER. • E-WS_2 shows the better electrocatalytic activity than bulk WS_2. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

  4. Boron-dependency of molybdenum boride electrocatalysts for the hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Park, Hyounmyung; Encinas, Andrew; Fokwa, Boniface P.T.; Scheifers, Jan P.; Zhang, Yuemei

    2017-01-01

    Molybdenum-based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo_2B, α-MoB, β-MoB, and MoB_2 by arc-melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X-ray photoelectron spectroscopy (XPS) for the first time; MoB_2 and β-MoB show excellent activity in the same range as the recently reported α-MoB and β-Mo_2C phases, while the molybdenum richest phase Mo_2B show significantly lower HER activity, indicating a strong boron-dependency of these borides for the HER. In addition, MoB_2 and β-MoB show long-term cycle stability in acidic solution. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Correlation between Gas Bubble Formation and Hydrogen Evolution Reaction Kinetics at Nanoelectrodes.

    Science.gov (United States)

    Chen, Qianjin; Luo, Long

    2018-04-17

    We report the correlation between H 2 gas bubble formation potential and hydrogen evolution reaction (HER) activity for Au and Pt nanodisk electrodes (NEs). Microkinetic models were formulated to obtain the HER kinetic information for individual Au and Pt NEs. We found that the rate-determining steps for the HER at Au and Pt NEs were the Volmer step and the Heyrovsky step, respectively. More interestingly, the standard rate constant ( k 0 ) of the rate-determining step was found to vary over 2 orders of magnitude for the same type of NEs. The observed variations indicate the HER activity heterogeneity at the nanoscale. Furthermore, we discovered a linear relationship between bubble formation potential ( E bubble ) and log( k 0 ) with a slope of 125 mV/decade for both Au and Pt NEs. As log ( k 0 ) increases, E bubble shifts linearly to more positive potentials, meaning NEs with higher HER activities form H 2 bubbles at less negative potentials. Our theoretical model suggests that such linear relationship is caused by the similar critical bubble formation condition for Au and Pt NEs with varied sizes. Our results have potential implications for using gas bubble formation to evaluate the HER activity distribution of nanoparticles in an ensemble.

  6. Symmetrical synergy of hybrid CoS2-WS2 electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng

    2017-06-05

    A highly active and stable hybrid electrocatalyst 3D hierarchical CoS2 nanosheets incorporated with WS2 (CoS2@WS2) has been developed via a one-step sulfurization method for the first time, where the contents of WS2 can be adjusted easily. We first prove the addition of small amounts of WS2 enhances the hydrogen evolution reaction (HER) performance of CoS2, and vise versa. In other words, we validated the symmetric synergy for HER between the Co- and W-based sulfide hybrid catalysts. In addition, we confirmed that the formation of nanointerfaces of Co-S-W between CoS2 and WS2 was responsible for the excellent HER activity (an overpotential of -97.2 mV at -10 mA/cm2, a small Tafel slope of 66.0 mV/dec, and prominent electrochemical stability) of hybrid electrocatalyst CoS2@WS2.

  7. Metallurgically prepared NiCu alloys as cathode materials for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Kunchan; Xia, Ming [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Xiao, Tao [2nd Xiangya Hospital, Central South University, Changsha 410011 (China); Lei, Ting, E-mail: tlei@mail.csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Yan, Weishan [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China)

    2017-01-15

    Ni−Cu bimetallic alloys with Cu content of 5, 10, 20, 30 and 50 wt% are prepared by powder metallurgy method, which consisted of powder mixing, pressing and sintering processes. The X-ray diffraction (XRD) measurement confirms that all the five Ni−Cu alloys possess the f.c.c. structure. The hydrogen evolution reaction (HER) activity of the prepared Ni−Cu alloy electrodes was studied in 6 M KOH solution by cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the electrocatalytic activity for the HER depended on the composition of Ni−Cu alloys, where Ni−10Cu alloy exhibited considerably higher HER activity than Ni plate and other Ni−Cu alloys, indicative of its chemical composition related intrinsic activity. - Highlights: • Ni−Cu alloys with various Cu contents were prepared by powder metallurgy method. • Ni−Cu alloy exhibits chemical composition related synergistic effect for HER activity. • Ni−10Cu alloy electrode presents a most efficient activity for HER. • Two time constants are observed in Nyquist curve and both of them related to the kinetics of HER.

  8. Hollow Pd/MOF Nanosphere with Double Shells as Multifunctional Catalyst for Hydrogenation Reaction.

    Science.gov (United States)

    Wan, Mingming; Zhang, Xinlu; Li, Meiyan; Chen, Bo; Yin, Jie; Jin, Haichao; Lin, Lin; Chen, Chao; Zhang, Ning

    2017-10-01

    A new type of hollow nanostructure featured double metal-organic frameworks shells with metal nanoparticles (MNPs) is designed and fabricated by the methods of ship in a bottle and bottle around the ship. The nanostructure material, hereinafter denoted as Void@HKUST-1/Pd@ZIF-8, is confirmed by the analyses of photograph, transmission electron microscopy, scanning electron microscopy, powder X-ray diffraction, inductively coupled plasma, and N 2 sorption. It possesses various multifunctionally structural characteristics such as hollow cavity which can improve mass transfer, the adjacent of the inner HKUST-1 shell to the void which enables the matrix of the shell to host and well disperse MNPs, and an outer ZIF-8 shell which acts as protective layer against the leaching of MNPs and a sieve to guarantee molecular-size selectivity. This makes the material eligible candidates for the heterogeneous catalyst. As a proof of concept, the liquid-phase hydrogenation of olefins with different molecular sizes as a model reaction is employed. It demonstrates the efficient catalytic activity and size-selectivity of Void@HKUST-1/Pd@ZIF-8. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Metallurgically prepared NiCu alloys as cathode materials for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Wang, Kunchan; Xia, Ming; Xiao, Tao; Lei, Ting; Yan, Weishan

    2017-01-01

    Ni−Cu bimetallic alloys with Cu content of 5, 10, 20, 30 and 50 wt% are prepared by powder metallurgy method, which consisted of powder mixing, pressing and sintering processes. The X-ray diffraction (XRD) measurement confirms that all the five Ni−Cu alloys possess the f.c.c. structure. The hydrogen evolution reaction (HER) activity of the prepared Ni−Cu alloy electrodes was studied in 6 M KOH solution by cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the electrocatalytic activity for the HER depended on the composition of Ni−Cu alloys, where Ni−10Cu alloy exhibited considerably higher HER activity than Ni plate and other Ni−Cu alloys, indicative of its chemical composition related intrinsic activity. - Highlights: • Ni−Cu alloys with various Cu contents were prepared by powder metallurgy method. • Ni−Cu alloy exhibits chemical composition related synergistic effect for HER activity. • Ni−10Cu alloy electrode presents a most efficient activity for HER. • Two time constants are observed in Nyquist curve and both of them related to the kinetics of HER.

  10. Production of hydrogen in the reaction between aluminum and water in the presence of NaOH and KOH

    Directory of Open Access Journals (Sweden)

    C. B. Porciúncula

    2012-06-01

    Full Text Available The objective of this work is to investigate the production of hydrogen as an energy source by means of the reaction of aluminum with water. This reaction only occurs in the presence of NaOH and KOH, which behave as catalysts. The main advantages of using aluminum for indirect energy storage are: recyclability, non-toxicity and easiness to shape. Alkali concentrations varying from 1 to 3 mol.L-1 were applied to different metallic samples, either foil (0.02 mm thick or plates (0.5 and 1 mm thick, and reaction temperatures between 295 and 345 K were tested. The results show that the reaction is strongly influenced by temperature, alkali concentration and metal shape. NaOH commonly promotes faster reactions and higher real yields than KOH.

  11. Adsorption of cadmium ions on nickel surface skeleton catalysts and its effect on reaction of cathodic hydrogen evolution

    International Nuclear Information System (INIS)

    Korovin, N.V.; Udris, E.Ya.; Savel'eva, O.N.

    1986-01-01

    Cadmium adsorption from different concentration CdSO 4 solutions on nickel surface skeleton catalysts (Ni ssc ) is studied by recording of polarization and potentiodynamic curves using electron microscopy and X-ray spectrometry. Main regularities of cadmium adsorption on Ni ssc are shown to be similar to those on smooth and skeleton nickel. A conclusion is drawn that increase of catalytic activity in reaction of cathodic hydrogen evolution from alkali solutions of Ni ssc base electrodes after their treatment in solutions containing Cd 2+ ions is due to irreversible desorption of strongly and averagely bound hydrogen from electrode surface at cadmium adsorption on them

  12. Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

    Science.gov (United States)

    Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

    2016-03-01

    Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

  13. Hydrogen Production From Water By Thermo-Chemical Methods (UT-3): Evaluation of Side Reactions By Simulation Process

    International Nuclear Information System (INIS)

    Rusli, A.

    1997-01-01

    Hydogen fuel with its advantages will be able to replace all the positions of fossil fuels post o il and gas or migas . Among the advantages of hydrogen fuel are pollution free, abundant of raw material in the form of water molecule, flexible in application, able to stroge and transport as well as fossil energy sources (oil and gas). Hydogen could be produced from water by means of thermochemical, thermolysis, photolysis and electrolysis. Nuclear heat (HTGR), solar heat or waste heat from steel industry can be used as energy source for these processes. In case of thermochemical method, some problems realated to production process should be studied and evaluated. Simulation is considered can be applied to study the effects of side reactions and also to resolve its problems in hydrogen production process. In this paper is reported the evalution results of hydrogen production process by thermochemical (UT-3) through both of the experimental and computer simulation. It has been proposed a new flow chart of hydrogen production to achieve the hydrogen production continuously. A simulator has been developed based on experimental data and related mathematical equations. This simulator can be used to scle-up the UT-3 thermochemical cycle for hydrogen production process

  14. Reaction mechanism of coal liquefaction: hydrogenolysis of model compound using synthetic pyrite as catalysts. 7. Property change of synthetic pyrite catalyst with the time after production; Sekitan ekika hanno kiko (model kagobutsu no hanno). 7. Gosei ryukatetsu shokubai no keiji henka ni tsuite

    Energy Technology Data Exchange (ETDEWEB)

    Ito, H.; Meno, H.; Uemaki, O.; Shibata, T.; Tsuji, T. [Hokkaido University, Sapporo (Japan)

    1996-10-28

    Reactions of various model compounds were investigated using synthetic pyrites for coal liquefaction. In this study, successive changes of the catalysts were investigated from the reactions of model compounds by using three different synthetic pyrites with the lapse of time after production. Benzyl phenyl ether, dibenzyl, and n-octylbenzene were used as model compounds. Reactions were conducted in an autoclave, into which sample, catalyst, decalin as solvent, and initial hydrogen pressure 10 MPa were charged. The autoclave was held at 450 or 475{degree}C of reaction temperature for 1 hour. The catalyst with a shorter lapse of time after production acted to hydrogen transfer, and inhibited the formation of condensation products due to the stabilization of decomposed fragment. It also acted to isomerization of materials by cutting alkyl side chains. When adding sulfur to the catalyst with longer lapse of time after production under these reaction conditions, it inhibited the formation of condensation products for the reaction of benzyl phenyl ether. However, it did not provide the effect for the reaction of n-octylbenzene. 5 refs., 3 figs.

  15. Hydrogen.

    Science.gov (United States)

    Bockris, John O'M

    2011-11-30

    The idea of a "Hydrogen Economy" is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO₂ in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H₂ from the electrolyzer. Methanol made with CO₂ from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  16. Hydrogen production from water gas shift reaction in a high gravity (Higee) environment using a rotating packed bed

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Hsin; Syu, Yu-Jhih [Department of Greenergy, National University of Tainan, Tainan 700 (China)

    2010-10-15

    Hydrogen production via the water gas shift reaction (WGSR) was investigated in a high gravity environment. A rotating packed bed (RPB) reactor containing a Cu-Zn catalyst and spinning in the range of 0-1800 rpm was used to create high centrifugal force. The reaction temperature and the steam/CO ratio ranged from 250 to 350 C and 2 to 8, respectively. A dimensionless parameter, the G number, was derived to account for the effect of centrifugal force on the enhancement of the WGSR. With the rotor speed of 1800 rpm, the induced centrifugal force acting on the reactants was as high as 234 g on average in the RPB. As a result, the CO conversion from the WGSR was increased up to 70% compared to that without rotation. This clearly revealed that the centrifugal force was conducive to hydrogen production, resulting from intensifying mass transfer and elongating the path of the reactants in the catalyst bed. From Le Chatelier's principle, a higher reaction temperature or a lower steam/CO ratio disfavors CO conversion; however, under such a situation the enhancement of the centrifugal force on hydrogen production from the WGSR tended to become more significant. Accordingly, a correlation between the enhancement of CO conversion and the G number was established. As a whole, the higher the reaction temperature and the lower the steam/CO ratio, the higher the exponent of the G number function and the better the centrifugal force on the WGSR. (author)

  17. Quasiclassical trajectory study of the molecular beam kinetics of the deuterium atom--hydrogen halide exchange reactions

    International Nuclear Information System (INIS)

    Raff, L.M.; Suzukawa, H.H. Jr.; Thompson, D.L.

    1975-01-01

    Unadjusted quasiclassical trajectory computations have been carried out to simulate the molecular beam scattering of thermal D atom beams at 2800 degreeK crossed with beams of HCl and HI at 250 degreeK. Total reaction cross sections, energy partitioning distributions, and differential scattering cross sections have been computed for the exchange reactions D+HCl → DCl+H and D+HI → DI+H while total reaction cross sections are reported for the corresponding abstractions, i.e., D+HCl → HD+Cl and D+HI → HD+I. For the exchange reactions, the computed reaction cross sections are within the range estimated from the crossed beam experiments. The calculated average energy partitioned into relative translational motion of products is in near quantitative agreement with the beam results, and the predicted differential scattering cross sections appear to be in qualitative accord with the beam experiments. The over-all agreement between theory and experiment indicates that previously computed values for the thermal rate coefficients for the exchange reactions are of the right order and that a systematic error exists in the interpretation of photolysis data in the hydrogen--hydrogen halide systems

  18. Report for fiscal 1994 by gasification technology subcommittee, Coal Gasification Committee; 1994 nendo sekitan gas ka iinkai gas ka gijutsu bukai hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-03-01

    As the result of a RUN-9 operation in the research on technologies for hydrogen production from coal and for pilot plants, it is found that the Muswellbrook, Datong, and Blair Athol coals are all suitable for gasification in pilot plants. Their handlability is considerably improved when the grain sizes after crushing are allowed to remain coarse (with the Blair Athol coal still retaining some disadvantage). A concept design is prepared for a HYCOL (hydrogen from coal) process demonstration plant. The reference coal is an imported coal similar to the Taiheiyo coal, and the hydrogen production target is set at 1-million m{sup 3}N/d (590t/d in terms of Taiheiyo coal) and hydrogen purity at 95% or higher. The whole process consists of coal gasification (with oxygen serving as gasification agent), dedusting, conversion to CO, desulfurization and decarboxylation (recovery of sulfur), and methanation. The gasification furnace is a 1-chamber entrained bed type with a 2-stage gyration flow. Dried and pulverized coal is conveyed aboard an air flow into the gasification furnace, where it is thrown into partial combustion reaction with the gasification agent for gasification in a high-temperature zone (1,500-1,600 degrees C), and the ash is taken out as slag. The generated gas is cooled in a heat recovery boiler, dedusted in a cyclone dust filter, and then forwarded to the washing unit. (NEDO)

  19. Coal background paper. Coal demand

    International Nuclear Information System (INIS)

    1997-01-01

    Statistical data are presented on coal demands in IEA and OECD member countries and in other countries. Coal coaking and coaking coal consumption data are tabulated, and IEA secretariat's coal demand projections are summarized. Coal supply and production data by countries are given. Finally, coal trade data are presented, broken down for hard coal, steam coal, coking coal (imports and export). (R.P.)

  20. Enhanced hydrogen reaction kinetics of nanostructured Mg-based composites with nanoparticle metal catalysts dispersed on supports

    International Nuclear Information System (INIS)

    Yoo, Yeong; Tuck, Mark; Kondakindi, Rajender; Seo, Chan-Yeol; Dehouche, Zahir; Belkacemi, Khaled

    2007-01-01

    Hydrogen reaction kinetics of nanocrystalline MgH 2 co-catalyzed with Ba 3 (Ca 1+x Nb 2-x )O 9-δ (BCN) proton conductive ceramics and nanoparticle bimetallic catalyst of Ni/Pd dispersed on single wall carbon nanotubes (SWNTs) support has been investigated. The nanoparticle bimetallic catalysts of Ni/Pd supported by SWNTs were synthesized based on a novel polyol method using NiCl 2 .6H 2 O, PdCl 2 , NaOH and ethylene glycol (EG). The nanostructured Mg composites co-catalyzed with BCN and bimetallic supported catalysts exhibited stable hydrogen desorption capacity of 6.3-6.7 wt.% H 2 and the significant enhancement of hydrogen desorption kinetics at 230-300 deg. C in comparison to either non-catalyzed MgH 2 or the nanocomposite of MgH 2 catalyzed with BCN

  1. Laboratory Studies of Hydrogen Gas Generation Using the Cobalt Chloride Catalyzed Sodium Borohydride-Water Reaction

    Science.gov (United States)

    2015-07-01

    already use hydrogen for weather balloons . Besides cost, hydrogen has other advantages over helium. Hydrogen has more lift than helium, so larger...of water vapor entering the gas stream, and avoid damaging the balloon /aerostat (aerostats typically have an operational temperature range of -50 to...Aerostats: “Gepard” Tethered Aerostats with Mobile Mooring Systems. Available at http://rosaerosystems.com/aero/obj7. Accessed June 4, 2015. 11

  2. Hydrogen evolution reaction at Ru-modified nickel-coated carbon fibre in 0.1 M NaOH

    Directory of Open Access Journals (Sweden)

    Pierożyński Bogusław

    2015-03-01

    Full Text Available The electrochemical activity towards hydrogen evolution reaction (HER was studied on commercially available (Toho-Tenax and Ru-modified nickel-coated carbon fibre (NiCCF materials. Quality and extent of Ru electrodeposition on NiCCF tows were examined by means of scanning electron microscopy (SEM. Kinetics of the hydrogen evolution reaction were investigated at room temperature, as well as over the temperature range: 20-50°C in 0.1 M NaOH solution for the cathodic overpotential range: -100 to -300 mV vs. RHE. Corresponding values of charge-transfer resistance, exchange current-density for the HER and other electrochemical parameters for the examined fibre tow composites were recorded.

  3. 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.

  4. Hydrogen

    Directory of Open Access Journals (Sweden)

    John O’M. Bockris

    2011-11-01

    Full Text Available The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan. Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  5. Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions

    Directory of Open Access Journals (Sweden)

    Georgios D. Papakonstantinou

    2011-01-01

    striking target issue of the present paper, has been shown to be the superior for substantiation of the revertible cell assembly for spontaneous reversible alterpolar interchanges between PEMFC and WE. The main target of the present thorough review study has been to throw some specific insight light on the overall spillover phenomena and their effects in electrocatalysis of oxygen and hydrogen electrode reactions from diverse angles of view and broad contemporary experimental methods and approaches (XPS, FTIR, DRIFT, XRD, potentiodynamic spectra, UHRTEM.

  6. The evaluation of the polarization resistance in a tubular electrode and its application to the hydrogen electrode reaction

    International Nuclear Information System (INIS)

    Montero, M.A.; Marozzi, C.A.; Chialvo, M.R. Gennero de; Chialvo, A.C.

    2007-01-01

    An alternative method for the determination of the kinetic parameters involved in the elementary steps of the reaction mechanism of the hydrogen electrode reaction is proposed. It is based on the determination of the variation of the polarization resistance in a tubular platinum electrode with a laminar flow of electrolyte as a function of the activity of protons of the electrolyte solution. A theoretical expression that relates the experimental variables and the equilibrium polarization resistance is developed, which takes into account the current distribution along the electrode surface. The results are compared with others obtained previously, contributing to the verification of the kinetic mechanism through a completely different experimental procedure

  7. Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

    Science.gov (United States)

    Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

    2014-12-08

    A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Hydrogen Oxidation Reaction at the Ni/YSZ Anode of Solid Oxide Fuel Cells from First Principles

    Science.gov (United States)

    Cucinotta, Clotilde S.; Bernasconi, Marco; Parrinello, Michele

    2011-11-01

    By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.

  9. A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy.

    Science.gov (United States)

    Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J

    2017-04-05

    The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.

  10. Optimization of hydrogen production via coupling of the Fischer-Tropsch synthesis reaction and dehydrogenation of cyclohexane in GTL technology

    International Nuclear Information System (INIS)

    Rahimpour, M.R.; Bahmanpour, A.M.

    2011-01-01

    In this study, a thermally-coupled reactor containing the Fischer-Tropsch synthesis reaction in the exothermic side and dehydrogenation of cyclohexane in the endothermic side has been modified using a hydrogen perm-selective membrane as the shell of the reactor to separate the produced hydrogen from the dehydrogenation process. Permeated hydrogen enters another section called permeation side to be collected by Argon, known as the sweep gas. This three-sided reactor has been optimized using differential evolution (DE) method to predict the conditions at which the reactants' conversion and also the hydrogen recovery yield would be maximized. Minimizing the CO 2 and CH 4 yield in the reactor's outlet as undesired products is also considered in the optimization process. To reach this goal, optimal initial molar flow rate and inlet temperature of three sides as well as pressure of the exothermic side have been calculated. The obtained results have been compared with the conventional reactor data of the Research Institute of Petroleum Industry (RIPI), the membrane dual - type reactor suggested for Fischer-Tropsch synthesis, and the membrane coupled reactor presented for methanol synthesis. The comparison shows acceptable enhancement in the reactor's performance and that the production of hydrogen as a valuable byproduct should also be considered.

  11. Hydrogen depth resolution in multilayer metal structures, comparison of elastic recoil detection and resonant nuclear reaction method

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S. E-mail: leszekw@optushome.com.au; Grambole, D.; Kreissig, U.; Groetzschel, R.; Harding, G.; Szilagyi, E

    2002-05-01

    Four different metals: Al, Cu, Ag and Au have been used to produce four special multilayer samples to study the depth resolution of hydrogen. The layer structure of each sample was analysed using 2 MeV He Rutherford backscattering spectrometry, 4.5 MeV He elastic recoil detection (ERD) and 30 MeV F{sup 6+} HIERD. Moreover the hydrogen distribution was analysed in all samples using H({sup 15}N, {alpha}{gamma}){sup 12}C nuclear reaction analysis (NRA) with resonance at 6.385 MeV. The results show that the best depth resolution and sensitivity for hydrogen detection are offered by resonance NRA. The He ERD shows good depth resolution only for the near surface hydrogen. In this technique the depth resolution is rapidly reduced with depth due to multiple scattering effects. The 30 MeV F{sup 6+} HIERD demonstrated similar hydrogen depth resolution to He ERD for low mass metals and HIERD resolution is substantially better for heavy metals and deep layers.

  12. The initial stages of the reaction between ZrCo and hydrogen studied by hot-stage microscopy

    International Nuclear Information System (INIS)

    Bloch, J.; Brill, M.; Ben-Eliahu, Y.; Gavra, Z.

    1998-01-01

    The development of hydride phase on the surface of ZrCo under 1 bar of hydrogen was investigated at temperatures between 75 and 300 C. Both surface modifications of the parent alloy and the nucleation and growth of hydride phase were observed. Surface modifications included: grain boundary outgrowth, intra-granular precipitation in the form of fine lamellar hydride phase and micro cracks. It is suggested that the surface modifications result from a combination of hydrogen solubility and the parent metal ductility. These modifications were enhanced near areas which had been previously transformed. The nucleation was self catalyzed, with new nuclei preferentially formed at the vicinity of growing former nuclei. All this suggested that the transport of hydrogen through the hydride phase is faster than its transfer through the surface passivation layer. The growth rate of the nuclei was similar to that of uranium. The activation energy for the growth was E a =24±3 kJ/mol. The results were compared with several other metal-hydrogen systems. It is suggested that the important physical factors controlling the mechanism of the initial hydriding reaction are hydrogen solubility and the brittleness of the parent metal/alloy. These parameters are responsible to the different changes observed during the initial hydriding stages which include: surface modifications, cracking, nucleation and growth. (orig.)

  13. Factors affecting hydrogen-tunneling contribution in hydroxylation reactions promoted by oxoiron(IV) porphyrin π-cation radical complexes.

    Science.gov (United States)

    Cong, Zhiqi; Kinemuchi, Haruki; Kurahashi, Takuya; Fujii, Hiroshi

    2014-10-06

    Hydrogen atom transfer with a tunneling effect (H-tunneling) has been proposed to be involved in aliphatic hydroxylation reactions catalyzed by cytochrome P450 and synthetic heme complexes as a result of the observation of large hydrogen/deuterium kinetic isotope effects (KIEs). In the present work, we investigate the factors controlling the H-tunneling contribution to the H-transfer process in hydroxylation reaction by examining the kinetics of hydroxylation reactions at the benzylic positions of xanthene and 1,2,3,4-tetrahydronaphthalene by oxoiron(IV) 5,10,15,20-tetramesitylporphyrin π-cation radical complexes ((TMP(+•))Fe(IV)O(L)) under single-turnover conditions. The Arrhenius plots for these hydroxylation reactions of H-isotopomers have upwardly concave profiles. The Arrhenius plots of D-isotopomers, clear isosbestic points, and product analysis rule out the participation of thermally dependent other reaction processes in the concave profiles. These results provide evidence for the involvement of H-tunneling in the rate-limiting H-transfer process. These profiles are simulated using an equation derived from Bell's tunneling model. The temperature dependence of the KIE values (k(H)/k(D)) determined for these reactions indicates that the KIE value increases as the reaction temperature becomes lower, the bond dissociation energy (BDE) of the C-H bond of a substrate becomes higher, and the reactivity of (TMP(+•))Fe(IV)O(L) decreases. In addition, we found correlation of the slope of the ln(k(H)/k(D)) - 1/T plot and the bond strengths of the Fe═O bond of (TMP(+•))Fe(IV)O(L) estimated from resonance Raman spectroscopy. These observations indicate that these factors modulate the extent of the H-tunneling contribution by modulating the ratio of the height and thickness of the reaction barrier.

  14. Gas-phase ion/molecule isotope-exchange reactions: methodology for counting hydrogen atoms in specific organic structural environments by chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    Hunt, D.F.; Sethi, S.K.

    1980-01-01

    Ion/molecule reactions are described which facilitate exchange of hydrogens for deuteriums in a variety of different chemical environments. Aromatic hydrogens in alkylbenzenes, oxygenated benzenes, m-toluidine, m-phenylenediamine, thiophene, and several polycyclic aromatic hydrocarbons and metallocenes are exchanged under positive ion CI conditions by using either D 2 O, EtOD, or ND 3 as the reagent gas. Aromatic hydrogens, benzylic hydrogens, and hydrogens on carbon adjacent to carbonyl groups suffer exchange under negative ion CI conditions in ND 3 , D 2 O, and EtOD, respectively. A possible mechanism for the exchange process is discussed. 1 figure, 2 tables

  15. Thermocatalytical processing of coal and shales

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

    Full Text Available The article investigates the questions of thermocatalytical conversion of organic mass of coal (OMC, it is shown that in the absence of a catalyst process is carried out by a radical process. Accumulated data on the properties for radicals of different structure and therefore different reaction capacity enables us to understand and interpret the conversion of OMC. Thermal conversion of OMC regarded as a kind of depolymerization, accompanied by decomposition of the functional groups with the formation of radicals, competing for hydrogen atom. Catalyst can change the direction and conditions of the process. Modern catalysts can reduce the process pressure up to 50 atm., with a high degree of coal conversion. We consider examples of simultaneous conversion of coal and shale, shale and masut, shale and tar.

  16. Study of hydrogen in metal and alloy by nuclear reaction channeling method

    International Nuclear Information System (INIS)

    Yagi, Eiichi

    1998-01-01

    The position of hydrogen in the lattice was determined by the combination method of 1 H( 11 B, α)αα with a channeling effect of 11 B ion in the crystal. When the concentration of hydrogen in V single crystal was VH 0.1 at the room temperature, hydrogen occupied T position in the body-centered cubic lattice. The position was shifted to the displaced-T by the thermal treatment. Hydrogen in V is oversensitive to a stress, so that it located the displaced-T or 4T state under 7 kg/mm 2 of compressive stress. Hydrogen in Nb and Ta located T position, too. But their displaced states were not observed by the thermal treatment. All hydrogen in Nb-3 at % Mo-2 at % H alloy were captured by Mo and they located the positions of 0.62A displaced from T in the direction of Mo. In Nb-3 at % Mo-5 at % H alloy, a part of hydrogen were captured by Mo, but the other located T positions. At 100degC, hydrogen was free from capture of Mo and moved to T position. (S.Y.)

  17. Characterization of catalytically hydrotreated coal liquid produced by solvolytic liquefaction in petroleum asphalt

    Energy Technology Data Exchange (ETDEWEB)

    Mochida, I.; Oishi, T.; Korai, Y.; Fujitsu, H.; Takeshita, K.

    1983-03-01

    A hydrotreated coal liquid produced by solvolytic liquefaction of a feed originally consisting of 66% petroleum asphalt and 34% coal liquid was characterized. The hydrotreatment was carried out over a Co-Mo catalyst in order to upgrade moderately and selectively the coal-derived fraction. The present process was found very effective to depolymerize rather selectively the coal-derived fraction, originally benzene insoluble, to be soluble in benzene in the dominant presence of petroleum asphalt, while 20% of the asphalt was converted to be distillable with ..cap alpha..-methylnaphthalene (the hydrotreatment solvent). Structural analyses of the fractions before and after hydrotreatment were compared to reveal what kinds of chemical reactions had taken place during hydro treatment. The major reactions of the coal derived fraction are hydrodeoxygenation and hydrodealkylation, both of which are effective for depolymerization. No significant hydrogenation on aromatic rings was observed. Hydrotreated liquid was further pyrolyzed to obtain oils and cokes of high quality. (14 refs.)

  18. Appearance of rapid carbon on hydrogasification of coal; Suiten gas ka ni okeru kokassei tanso no hatsugen

    Energy Technology Data Exchange (ETDEWEB)

    Soneda, Y.; Makino, M. [National Institute for Resources and Environment, Tsukuba (Japan)9] Xu, W. [New Energy and Industrial Technology Development Organization, Tokyo, (Japan)

    1998-09-20

    The technology of hydrogasification of coal now under development under a State project aims to produce light oil as well as methane-rich high calorie gas through the direct reaction between coal and hydrogen, and is expected to deal with the difficult natural gas demand/supply relationship anticipated for the future. Although it is mandatory to fully understand the reaction between coal and hydrogen for the completion of this technology, yet there are many tasks to be fulfilled. One of the tasks is the elucidation of the behavior of what is named rapid carbon that appears upon the rapid heating of coal in a high-pressure hydrogen environment. In this paper, some interesting findings about the appearance of rapid carbon are reported. When coal is placed in such an environment, volatile components are lost first of all and then the active carbon reaction occurs. When the behavior of active carbon in the reaction is observed, it is found that active carbon is not so small in quantity, and the result of observation of its appearance and deactivation during the reaction justifies an inference that the reaction is regarded as one of the primary reactions in the process of hydrogasification. Accordingly, systematic studies of its physical and chemical features from various viewpoints are necessary. 5 refs., 3 figs., 1 tab.

  19. Depolymerization of coal by oxidation and alkylation; Sanka bunkai to alkyl ka ni yoru sekitan kaijugo

    Energy Technology Data Exchange (ETDEWEB)

    Tomita, H.; Isoda, T.; Kusakabe, K.; Morooka, S. [Kyushu University, Fukuoka (Japan). Faculty of Engineering; Hayashi, J. [Hokkaido University, Sapporo (Japan). Center for Advanced Research of Energy Technology

    1996-10-28

    Change in depolymerization degree and coal structure was studied for depolymerization treatment of coal in various alcohol containing aqueous hydrogen peroxide. In experiment, the mixture of Yallourn coal, alcohol and aqueous hydrogen peroxide was agitated in nitrogen atmosphere of normal pressure at 70{degree}C for 12 hours. As the experimental result, the methanol solubility of only 5% of raw coal increased up to 35.2% by hydrogen peroxide treatment, while the yield of insoluble matters also decreased from 94% to 62%. Most of the gas produced during treatment was composed of inorganic gases such as CO and CO2, and its carbon loss was extremely decreased by adding alcohol. From the analytical result of carbon loss in hydrogen peroxide treatment, it was clarified that alkylation advances with introduction of alkyl group derived from alcohol into coal by hydrogen peroxide treatment under a coexistence of alcohol, and depolymerization reaction of coal itself is thus promoted by alcohol. 4 refs., 7 figs., 1 tab.

  20. Supercritical water gasification of Victorian brown coal: Experimental characterisation

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, Doki; Aye, Lu [Department of Civil and Environmental Engineering, The University of Melbourne, Vic 3010 (Australia); Sanderson, P. John; Lim, Seng [CSIRO Minerals, Clayton, Vic 3168 (Australia)

    2009-05-15

    Supercritical water gasification is an innovative thermochemical conversion method for converting wet feedstocks into hydrogen-rich gaseous products. The non-catalytic gasification characteristics of Victorian brown coal were investigated in supercritical water by using a novel immersion technique with quartz batch reactors. Various operating parameters such as temperature, feed concentration and reaction time were varied to investigate their effect on the gasification behaviour. Gas yields, carbon gasification efficiency and the total gasification efficiency increased with increasing temperature and reaction time, and decreasing feed concentration. The mole fraction of hydrogen in the product gases was lowest at 600 C, and increased to over 30 % at a temperature of 800 C. Varying parameters, especially reaction time, did not improve the coal utilisation for gas production significantly and the measured data showed a large deviation from the equilibrium level. (author)

  1. 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

  2. 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.

  3. Induction of interleukin-6 by coal containing bioavailable iron is ...

    Indian Academy of Sciences (India)

    Unknown

    Coal mining causes health problems, such as pneumoconiosis. We have ... levels. The enhancing effect on the IL-6 by the PA coal was similar to that caused by hydrogen peroxide. ..... stress: possible implications in coal workers' lung disease;.

  4. Fiscal 1999 research cooperation project report. Research cooperation on coal liquefaction technology; 1999 nendo sekitan ekika gijutsu ni kansuru kenkyu kyoryoku jigyo

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    This report summarizes the fiscal 1999 research cooperation project result on coal liquefaction technology. Cooperative FS was made on coal liquefaction technology of Indonesian coal as petroleum substituting energy. To obtain the basic data necessary for the FS, study was made on the applicability of Indonesian natural minerals as catalytic materials. Promising low-cost abundant Soroako Limonite ore showed a high catalytic activity for liquefaction reaction of Banko coal, and an excellent grindability. Improved BCL process including hydrogenation process was promising for production of high-quality coal liquid superior in storage stability with less nitrogen and sulfur contents. Survey was made on the general conditions of Tanjung Enim area including South Banko coal field concerned, and the geological features and coal seam of South Banko coal field which is composed of 3 seams including coal deposits of 6.35 hundred million tons. To study the marketability of coal liquid, survey was made on the current situation of oil, oil product standards, and blendability of coal liquid. Hydrogen for the liquefaction process can be obtained by coal gasification. (NEDO)

  5. Reaction of hydrogen atoms produced by radiolysis and photolysis in solid phase at 4 and 77 K

    International Nuclear Information System (INIS)

    Miyazaki, Tetsuo

    1991-01-01

    The behavior of H atoms in the solid phase has been reviewed with special attention to comparison of H atoms produced by radiolysis with those produced by photolysis. The paper consists of three parts. I -Production of H atoms: (1) the experimental results which indicate H-atom formation in the radiolysis of solid alkane are summarized; (2) ESR saturation behavior of trapped H atoms depends upon the method of H-atom-production, i.e. photolysis or radiolysis, and upon the initial energy of H atoms in the photolysis. II - Diffusion of H atoms: (1) activation energies for thermally-activated diffusion of H atoms are shown; (2) quantum diffusion of H atoms in solid H 2 is explained in terms of repetition of tunneling reaction H 2 + H → H + H 2 . III -Reaction of H atoms: (1) reactions and trapping processes of hot H atoms have been shown in solid methane and argon by use of hot H atoms with specified initial energy; (2) when H atoms are produced by the radiolysis of solvent alkane or by the photolysis of HI in the alkane mixtures at 77 K, the H atoms react very selectively with solute alkane at low concentration. The selective reaction of the H atom has been found in eight matrices; (3) activation energy for a hydrogen-atom-abstraction reaction by thermal H atoms at low temperatures is less than than several kJ mol -1 because of quantum tunneling. The absolute rate constants for H 2 (D 2 , HD) + H(D) tunneling reactions have been determined experimentally in solid hydrogen at 4.2K; (4) theoretical studies for tunneling reactions H 2 (D 2 ,HD) + H(D) at ultralow temperatures were reviewed. The calculated rate constants were compared with the rate constants obtained experimentally. (author)

  6. Achievement report for fiscal 1982 on Sunshine Program. Coal energy; 1982 nendo sunshine keikaku seika hokokusho. Sekitan energy

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1982-07-01

    This research program consists of (1) the solid catalyst-aided reforming of various petroleum based oils and heavy coal oils into Solvolysis solvents and the secondary hydrogenolysis, (2) a search for pre-treatment for improvement on the sub-bituminous coal liquefaction yield, and (3) a search for measures for improvement on the brown coal liquefaction yield. Studied in this fiscal year are (1) the high-temperature short-contact time liquefaction of brown coal, (2) the role of catalyst support for selective upgrading of SRC (solvent refined coal), and (3) reforming of thermal melting feature of low rank coal by preliminary deashing at room temperature. In relation with Item (1), it is found that the dehydrogenation or reaction to carbonization of molecules involved in hydrogen donation is structure-sensitive but that thermolysis of coal is accelerated under high-temperature conditions to allow transfer hydrogen to contribute uniformly. It is deemed also that matching is excellent between hydrogen transfer and thermolysis, that the solvent dissolution level is elevated, and that the reaction short in duration inhibits consecutive polymerization reaction. These are supposed to be effective in improving on the liquefaction yield and in rendering heavy constituents lighter. In relation with Item (2), it is found that the experimentally manufactured catalysts are effective in reducing the weight of heavy constituents. In relation with Item (3), a carbonization reforming method is experimentally implemented in which the ash that affects carbonization is further removed by a pre-treatment at room temperature. (NEDO)

  7. On the importance of hydrogen bonding in the promotion of Diels-Alder reactions of unactivated aldehydes: a computational study

    Science.gov (United States)

    Chemouri, Hafida; Mekelleche, Sidi Mohamed

    2014-03-01

    The kinetic solvent effects on the Diels-Alder (DA) reaction of N,N-dimethylamino-3-trimethylsilyl butadiene with p-anisaldehyde are studied by density functional calculations at the B3LYP/6-31C(d) level of theory. Experimentally, it has been found that the acceleration of this reaction is not due to the increase of the polarity of the solvent but it is rather due to hydrogen bonding (HB). Intrinsic reaction coordinate calculations combined with electron localisation function analysis show that this reaction follows a one-step two-stage mechanism with a highly asynchronous sigma bond formation process. The calculations, performed using an explicit solvent model based on the coordination of the carbonyl group with one molecule of the solvent, show a considerable decrease of the activation energy when going from the gas phase (ɛ = 1) to solution phase and this diminution is found to be more important in isopropyl alcohol (ɛ = 18.3) in comparison with acetonitrile (ɛ = 37.5). Our calculations also show that the acceleration of this DA reaction is due to the increase of the electrophilicity power of the solvated carbonyl compound and consequently the increase of the polarity of the reaction in the presence of protic solvents. The obtained results put in evidence the relevance of HB in the promotion of DA reactions of unactivated ketones as experimentally expected.

  8. MOF-derived Cu/nanoporous carbon composite and its application for electro-catalysis of hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Raoof, Jahan-Bakhsh; Hosseini, Sayed Reza; Ojani, Reza; Mandegarzad, Sakineh

    2015-01-01

    In this work, metal-organic framework Cu_3(BTC)_2 [BTC = 1,3,5-benzenetricarboxylate] (commonly known as MOF-199 or HKUST-1), is used as porous template for preparation of a Cu/nanoporous carbon composite. The MOF-derived Cu/nanoporous carbon composite (Cu/NPC composite) is synthesized by direct carbonization of the MOF-199 without any carbon precursor additive. The physical characterization of the solid catalyst is achieved by using a variety of different techniques, including XRD (X-ray powder diffraction), scanning electron microscopy, thermo-gravimetric analysis, and nitrogen physisorption measurements. The electrochemical results have shown that the Cu/NPC composite modified glassy carbon electrode (Cu/NPC/GCE) as a non-platinum electrocatalyst exhibited favorable catalytic activity for hydrogen evolution reaction, in spite of high resistance to faradic process. This behavior can be attributed to existence of Cu metal confirmed by XRD and/or high effective pore surface area (1025 m"2 g"−"1) in the Cu/NPC composite. The electron transfer coefficient and exchange current density for the Cu/NPC/GCE is calculated by Tafel plot at about 0.34 and 1.2 × 0"−"3 mAcm"−"2, respectively. - Graphical abstract: Metal organic framework-derived Cu/nanoporous carbon composite (Cu/NPC composite) was prepared by direct carbonization of MOF-199 without addition of any carbon source at 900 °C. The Cu/NPC/GCE demonstrated an excellent electrocatalytic activity towards hydrogen evolution reaction compared with bare GCE. - Highlights: • MDNPC (MOF-199 derived nanoporous carbon) is prepared by direct carbonization. • MOF-199 is utilized as a template without addition of carbon resource. • The MDNPC has a good electrocatalytic activity in hydrogen evolution reaction. • High BET surface area and hydrogen adsorption property improved catalyst activity.

  9. 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.

  10. Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

    Science.gov (United States)

    Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

    2018-03-01

    Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

  11. Report for fiscal 1981 of Sunshine Program coal group. Basic research on Solvolysis liquefaction technology; 1981 nendo solvolysis ekika gijutsu no kiso kenkyu hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1982-03-01

    Basic research is conducted on the Solvolysis liquefaction process for the purpose of producing from coal an ashless, low-sulfur, pollution-free liquid fuel. In the research on the Solvolysis liquefaction (1st stage liquefaction) of coal using a hydrogenation solvent, the Solvolysis liquefaction of coal is studied, for which a refined Solvolysis pitch containing coal substances and a hydride of solvent refined coal are used as Solvolysis liquefaction solvents for the 1st stage. In the research on the 1st stage liquefaction reaction conditions using a high-temperature closed process, two methods are employed. One is a method that uses a mini-pump type reactor in which a small hermetic container is submerged in a high-temperature solvent for rapid heating and the other is a method that uses a pipe type reactor in which coal slurry is caused to travel through a pipe heated to a high temperature. For the analysis of the 2nd stage liquefaction (hydrogenation) reaction conditions, the properties of the 2nd coal liquid, and the constitution of the 2nd coal liquid, and the for the research on the 1st stage liquefaction capacity, the hydrogenation of anthracene oil and solvent refined coal as recyclable solvent models is studied. (NEDO)

  12. Pressure hydrogenation of solid carbonaceous material

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M; Kroenig, W

    1942-09-28

    A process is described for the continuous pressure hydrogenation of solid, nonfusible carbonaceous material, such as coal, oil shale, or peat, in a pasted condition, characterized in that the charge is heated in a known way under pressure, together with water, nearly to the reaction temperature, then it is led into a pressure vessel, whose volume amounts to 20 to 40% of the usual reaction space without any change at the same temperature, and the charge then goes through the reaction vessel, after which its temperature is raised to the reaction height.

  13. Effects of neutral sodium hydrogen phosphate on setting reaction and mechanical strength of hydroxyapatite putty.

    Science.gov (United States)

    Ishikawa, K; Miyamoto, Y; Takechi, M; Ueyama, Y; Suzuki, K; Nagayama, M; Matsumura, T

    1999-03-05

    The setting reaction and mechanical strength in terms of diametral tensile strength (DTS) of hydroxyapatite (HAP) putty made of tetracalcium phosphate, dicalcium phosphate anhydrous, and neutral sodium hydrogen phosphate (Na1.8H1.2PO4) solution containing 8 wt % sodium alginate were evaluated as a function of the Na1.8H1.2PO4 concentration. In one condition, HAP putty was placed in an incubator kept at 37 degrees C and 100% relative humidity. In the other condition, immediately after mixing HAP putty was immersed in serum kept at 37 degrees C. Longer setting times and lower DTS values were observed when HAP putty was immersed in serum regardless of the Na1.8H1.2PO4 concentration. The setting times of the HAP putty in both conditions became shorter with an increase in the Na1. 8H1.2PO4 concentration, reaching approximately 7-13 min when the Na1. 8H1.2PO4 concentration was 0.6 mol/L or higher. The DTS value of HAP putty was relatively constant (10 MPa) regardless of the Na1.8H1. 2PO4 concentration (0.2-1.0 mol/L) when HAP putty was kept in an incubator. In contrast, when HAP putty was immersed in serum, the DTS value was dependent on the Na1.8H1.2PO4 concentration. It increased with the Na1.8H1.2PO4 concentration and reached approximately 5 MPa when the Na1.8H1.2PO4 concentration was 0.6 mol/L, after which it showed a relatively constant DTS value. We therefore would recommend a HAP putty that uses 0.6 mol/L Na1.8H1. 2PO4 since at that concentration the putty's setting time (approximately 10 min) is proper for clinical use and it shows good DTS value (approximately 5 MPa) even when it is immersed in serum immediately after mixing. Copyright 1999 John Wiley & Sons, Inc.

  14. Shape transformation of silver nanospheres to silver nanoplates induced by redox reaction of hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Parnklang, Tewarak; Lamlua, Banjongsak; Gatemala, Harnchana; Thammacharoen, Chuchaat [Department of Chemistry, Faculty of Science, Chulalongkorn University, 254 Phyathai Road, Patumwan, Bangkok 10330 (Thailand); Kuimalee, Surasak [Industrial Chemistry and Textile Technology Programme, Faculty of Science, Maejo University, Chiang Mai 50290 (Thailand); Lohwongwatana, Boonrat [Metallurgical Engineering Department, Faculty of Engineering, Chulalongkorn University, 254 Phyathai Road, Patumwan, Bangkok 10330 (Thailand); Ekgasit, Sanong, E-mail: sanong.e@chula.ac.th [Department of Chemistry, Faculty of Science, Chulalongkorn University, 254 Phyathai Road, Patumwan, Bangkok 10330 (Thailand)

    2015-03-01

    In this paper we demonstrate a simple and rapid shape transformation of silver nanospheres (AgNSs) to silver nanoplates (AgNPls) using the oxidation and reduction capabilities of hydrogen peroxide. AgNPls having tunable surface plasmon resonance across the visible region with average size of 40–100 nm and thickness of 10–15 nm can be fabricated within 2 min simply by adding H{sub 2}O{sub 2} into a colloid of AgNSs with average particle size of 7 nm. The efficiency of H{sub 2}O{sub 2} as a shape-transforming agent depends strongly on its concentration, pH of the AgNS colloid, and the employed stabilizers. H{sub 2}O{sub 2} oxidizes AgNSs to silver ions while concertedly reduces silver ions to silver atom necessary for the growth of AgNPls. The shape transformation reaction was conducted at a relatively low concentration of H{sub 2}O{sub 2} in order to minimize the oxidative dissolution while facilitating kinetically controlled growth of AgNPls under a near neutral pH. Polyvinyl-pyrrolidone is an effective steric stabilizer preventing aggregation while assisting the growth of AgNPls. Trisodium citrate inhibits the formation of AgNPls under the H{sub 2}O{sub 2} reduction as it forms a stable complex with silver ions capable of withstanding the weakly reducing power of H{sub 2}O{sub 2}. After a complete consumption of AgNSs, large nanoplates grows with an expense of smaller nanoplates. The growth continues until H{sub 2}O{sub 2} is exhausted. A high concentration H{sub 2}O{sub 2} promotes catalytic decomposition of H{sub 2}O{sub 2} on the surface of AgNSs and oxidative dissolution of AgNSs without a formation of AgNPls. - Graphical abstract: Proposed mechanism for the shape transformation of AgNSs to AgNPls induced by the oxidation/reduction of H{sub 2}O{sub 2}. - Highlights: • Rapid shape transformation of silver nanospheres to nanoplates by H{sub 2}O{sub 2}. • Structural change completes in 2 min with a yellow-to-blue color change. • Selective fabrication of

  15. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    KAUST Repository

    Michalak, William D.; Krier, James M.; Komvopoulos, Kyriakos; Somorjai, Gabor A.

    2013-01-01

    hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical

  16. Coal gasification. Quarterly report, January--March 1977

    Energy Technology Data Exchange (ETDEWEB)

    None

    1977-12-01

    High-Btu natural gas has a heating value of 950 to 1,000 Btu per standard cubic foot, is composed essentially of methane, and contains virtually no sulfur, carbon monoxide, or free hydrogen. The conversion of coal to high-Btu gas requires a chemical and physical transformation of solid coal. However, because coal has widely differing chemical and physical properties, depending on where it is mined, it is difficult to process. Therefore, to develop the most suitable techniques for gasifying coal, ERDA, together with the American Gas Association is sponsoring the development of several advanced conversion processes. Although the basic coal-gasification chemical reactions are the same for each process, the processes under development have unique characteristics. A number of the processes for converting coal to high Btu and to low Btu gas have reached the pilot plant stage. The responsibility for designing, constructing and operating each of these pilot plants is defined and progress on each during the quarter is described briefly. The accumulation of data for a coal gasification manual and the development of mathematical models of coal gasification processes are reported briefly. (LTN)

  17. Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

    Science.gov (United States)

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

  18. Functionalization of Hydrogenated Chemical Vapour Deposition-Grown Graphene by On-Surface Chemical Reactions

    Czech Academy of Sciences Publication Activity Database

    Drogowska, Karolina; Kovaříček, Petr; Kalbáč, Martin

    2017-01-01

    Roč. 23, č. 17 (2017), s. 4022-4022 ISSN 1521-3765 Institutional support: RVO:61388955 Keywords : Chemical vapor deposition * Hydrogenation * Graphene Subject RIV: CF - Physical ; Theoretical Chemistry

  19. Deuterium exchange reaction between hydrogen and water in a trickle-bed column packed with novel catalysts

    International Nuclear Information System (INIS)

    Ahn, D. H.; Baek, S. W.; Lee, H. S.; Kim, K. R.; Kang, H. S.; Lee, S. H.; Jeong, H. S.

    1998-01-01

    The activity of a novel catalyst (Pt/SDBC) for deuterium exchange reaction between water and hydrogen streams in a trickle bed was measured. The performance of the catalyst was compared with a commercial catalyst with same metal content. The catalytic activity for the bed of wet-proofed catalyst diluted with hydrophillic packing material also measured. The Pt/SDBC catalyst shows higher activity in the liquid phase reaction than the commercial catalyst as measured in the vapor phase reaction. The performance for 50% dilution of the Pt/SDBC catalyst bed with hydrophillic packing material is better than that of the 100% bed due to more liquid holdup and better water distribution

  20. Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

    DEFF Research Database (Denmark)

    Musko, Nikolai; Jensen, Anker Degn; Baiker, Alfons

    2012-01-01

    Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were...... cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved...... performed using a 5wt% Pd on activated carbon in custom-designed high pressure autoclaves at 323K. The Cubic-Plus-Association (CPA) equation of state was employed to model the phase behaviour of the experimentally studied systems. CPA binary interaction parameters were estimated based on the experimental...

  1. Hydrotreating NiMo/sepiolite catalysts: influence of catalyst preparation on activity for HDS, hydrogenation and chain isomerization reactions

    International Nuclear Information System (INIS)

    Melo, F.V.; Sanz, E.; Corma, A.; Mifsud, A.

    1987-01-01

    A series of NiMo catalysts supported on a sepiolite: a) in its natural state, b) modified by acid leaching, and c) modified by cation exchange, have been prepared. The preparation variables studied were: Method of metal deposition, amount of active phase, sepiolite pretreatment, and temperature and time of sulfurization. The catalytic activity for HDS, hydrogenation, and cracking-isomerization has been studied by feeding a thiophene-cyclohexene-cyclohexane mixture and carrying out the reaction in the following conditions: 300 0 and 400 0 C reaction temperature, 20 Kg.cm -2 total pressure, and 3 to 1 molar ratio of H 2 to hydrocarbons. An optimium for HDS and hydrogenation activity was found for a 12% wt MoO 3 , and 5% wt NiO, prepared by simultaneous impregnation by the pore volume method at Ph = 5.0. The optimum conditions with these catalysts are 400 0 C and 3 hours of sulfurization. An increase in the acidity of the support produces a decrease of HDS and hydrogenation and an increase of the cracking-isomerization activities. A good correlation between HDS and the concentration of an XNiO.MoO 3 phase is found. The XNiO.MoO 3 phase is completely sulfurized to a modified MoS 2 , while NiMoO 4 and MoO 3 are only slightly sulfurized. 31 refs.; 7 figs.; 1 table

  2. The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

    DEFF Research Database (Denmark)

    Knap, Hasse Christian

    a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

  3. Chemistry and catalysis of coal liquefaction, catalytic and thermal upgrading of coal liquid and hydrogenation of CO to produce fuels. Quarterly progress report, April-June 1980

    Energy Technology Data Exchange (ETDEWEB)

    Wiser, W.H.

    1980-01-01

    Systematic hydrodeoxygenation (HDO) studies of polycyclic ketones, e.g., 1-tetralone (1) and 2-tetralone (2) were carried out. The change in product composition as a function of sulfided catalyst type, reaction temperature, and contact time were investigated and feasible mechanistic schemes were developed. The hydrodenitrogenation (HDN) of acridine, a compound representative of linear N-containing polycyclics with a middle pyridine ring, was investigated. Results obtained show that at least two aromatic rings in the acridine system must be saturated before removal of the nitrogen atom from the middle ring could be effected. The catalytic cracking of 9,10-dihydronaphthalene was systematically investigated and a feasible mechanistic scheme for the reactions involved was developed. The study demonstrates that conventional zeolite-containing catalysts are ineffective for cracking of a middle hydroaromatic ring, flanked by two aromatic rings. Cracking of a middle hydroaromatic ring with such catalysts is effected only if the ring is flanked by at least another hydroaromatic ring, as in 1,2,3,4,9,10,11,12-octahydrophenanthrene. Studies on the effect of deactivation of commercial CoMo/Al/sub 2/O/sub 3/ catalysts by pyridine poisoning and by coke showed that the remaining active sites were essentially identical in character to those on the fresh catalyst. Thus, deactivation causes loss of some sites, but does not affect the activity of the remaining sites. Pyridine was much more effective in deactivating the catalyst than coke on a weight basis.

  4. The effect of urea on microstructures of Ni{sub 3}S{sub 2} on nickel foam and its hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jinlong, Lv, E-mail: ljltsinghua@126.com [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China); Tongxiang, Liang, E-mail: txliang@mail.tsinghua.edu.cn [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China)

    2016-11-15

    The effects of urea concentration on microstructures of Ni{sub 3}S{sub 2}formed on nickel foam and its hydrogen evolution reaction were investigated. The Ni{sub 3}S{sub 2} nanosheets with porous structure were formed on nickel foam during hydrothermal process due to low urea concentration. While high urea concentration facilitated the forming of Ni{sub 3}S{sub 2} nanotube arrays. The resulting Ni{sub 3}S{sub 2} nanotube arrays exhibited higher catalytic activity than Ni3S2nanosheets for hydrogen evolution reaction. This was mainly attributed to a fact that Ni{sub 3}S{sub 2} nanotube arrays facilitated diffusion of electrolyte for hydrogen evolution reaction. - Graphical abstract: The resulting Ni{sub 3}S{sub 2} nanotube arrays exhibited higher catalytic activity than Ni{sub 3}S{sub 2} nanosheets for hydrogen evolution reaction. This was mainly attributed to a fact that Ni{sub 3}S{sub 2} nanotube arrays facilitated diffusion of electrolyte for hydrogen evolution reaction and hydrogen evolution. - Highlights: • Urea promoted to forming more Ni{sub 3}S{sub 2} nanotube arrays on nickel foam. • Ni{sub 3}S{sub 2} nanotube arrays showed higher catalytic activity in alkaline solution. • Ni{sub 3}S{sub 2} nanotube arrays promoted electron transport and reaction during the HER.

  5. A Study on the Pressure-Composition Isotherm for the Reaction of ZrCo with Hydrogen

    International Nuclear Information System (INIS)

    Kim, Sunmi; Paek, Seungwoo; Lee, Minsoo; Kim, Sihyung; Kim, Kwangrag; Ahn, Dohee; Sohn, Soonhwan; Song, Kyumin

    2007-01-01

    The intermetallic compound of ZrCo which is one of the promising getters for the handling, transport, and storage of tritium has been extensively studied and widely used due to its attractive properties as a tritium getter. At a typical storage temperature of room temperature, the ZrCo-H system has an equilibrium pressure of about 10 -3 Pa for an absorption. The immobilized gas can be recovered at a moderate temperature. Also, from the point of view of safety, the ZrCo and its hydrides have proven to be much less pyrophoric than uranium and its hydrides are the most widely used as a tritium getter. In the current study, the pressure-composition isotherm for the reaction of ZrCo with hydrogen was derived to evaluate its absorption and release characteristics. This provides useful information on the stability and the storage capabilities of ZrCo and the subsequent release of the hydrogen on a heating

  6. A Study on the Pressure-Composition Isotherm for the Reaction of ZrCo with Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sunmi; Paek, Seungwoo; Lee, Minsoo; Kim, Sihyung; Kim, Kwangrag; Ahn, Dohee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Sohn, Soonhwan; Song, Kyumin [Electric Power Research Institute, Daejeon (Korea, Republic of)

    2007-10-15

    The intermetallic compound of ZrCo which is one of the promising getters for the handling, transport, and storage of tritium has been extensively studied and widely used due to its attractive properties as a tritium getter. At a typical storage temperature of room temperature, the ZrCo-H system has an equilibrium pressure of about 10{sup -3} Pa for an absorption. The immobilized gas can be recovered at a moderate temperature. Also, from the point of view of safety, the ZrCo and its hydrides have proven to be much less pyrophoric than uranium and its hydrides are the most widely used as a tritium getter. In the current study, the pressure-composition isotherm for the reaction of ZrCo with hydrogen was derived to evaluate its absorption and release characteristics. This provides useful information on the stability and the storage capabilities of ZrCo and the subsequent release of the hydrogen on a heating.

  7. Coal-to-liquid

    Energy Technology Data Exchange (ETDEWEB)

    Cox, A.W.

    2006-03-15

    With crude oil prices rocketing, many of the oil poor, but coal rich countries are looking at coal-to-liquid as an alternative fuel stock. The article outlines the two main types of coal liquefaction technology: direct coal liquefaction and indirect coal liquefaction. The latter may form part of a co-production (or 'poly-generation') project, being developed in conjunction with IGCC generation projects, plus the production of other chemical feedstocks and hydrogen. The main part of the article, based on a 'survey by Energy Intelligence and Marketing Research' reviews coal-to-liquids projects in progress in the following countries: Australia, China, India, New Zealand, the Philippines, Qatar and the US. 2 photos.

  8. Increase in extraction yields of coals by water treatment

    Energy Technology Data Exchange (ETDEWEB)

    Masashi Iino; Toshimasa Takanohashi; Chunqi Li; Haruo Kumagai [National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Institute for Energy Utilization

    2004-10-01

    The effect of water treatment at 500 and 600 K on solvent extractions of Pocahontas No. 3 (PO), Upper Freeport (UF), and Illinois No. 6 (IL) coals was investigated. All the coals used show that the water treatments at 600 K increased the extraction yields greatly in the extractions with a 1:1 carbon disulfide/N-methyl-2-pyrrolidinone (CS{sub 2}/NMP) mixed solvent, NMP, or 1-methylnaphthalene (1-MN). However, the water treatments at 500 K and the heat treatments at 600 K without water gave only a slight increase in the yields. Characterizations of the water-treated coals were performed using ultimate and proximate compositions, Fourier transform infrared analysis, solvent swelling, nuclear magnetic resonance relaxation time, and viscoelasticity behavior. The swelling degree in methanol and toluene was increased by the water treatment at 600 K, suggesting that crosslinks become loosened by the treatment. The results of infrared analysis and the extraction temperature dependency of the extraction yields with NMP and 1-MN suggest that the loosening of {pi} - interactions, and of both {pi} - interactions and hydrogen bonds, are responsible for the yield enhancements for PO and UF coals, respectively. However, for IL coal, which exhibited a decrease in oxygen content and the amount of hydrogen-bonded OH, suggesting the occurrence of some chemical reactions, the yield enhancements may be due to the relaxation of hydrogen bonds and the removal of oxygen functional groups, such as the breaking of ether bonds. 17 refs., 3 figs., 5 tabs.

  9. First Principles Based Simulation of Reaction-Induced Phase Transition in Hydrogen Storage and Other Materials

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Qingfeng [Southern Illinois Univ., Carbondale, IL (United States)

    2014-08-31

    This major part of this proposal is simulating hydrogen interactions in the complex metal hydrides. Over the period of DOE BES support, key achievements include (i) Predicted TiAl3Hx as a precursor state for forming TiAl3 through analyzing the Ti-doped NaAlH4 and demonstrated its catalytic role for hydrogen release; (ii) Explored the possibility of forming similar complex structures with other 3d transition metals in NaAlH4 as well as the impact of such complex structures on hydrogen release/uptake; (iii) Demonstrated the role of TiAl3 in hydriding process; (iv) Predicted a new phase of NaAlH4 that links to Na3AlH6 using first-principles metadynamics; (v) Examined support effect on hydrogen release from supported/encapsulated NaAlH4; and (vi) Expanded research scope beyond hydrogen storage. The success of our research is documented by the peer-reviewed publications.

  10. Kinetic Models Study of Hydrogenation of Aromatic Hydrocarbons in Vacuum Gas Oil and Basrah Crude Oil Reaction

    Directory of Open Access Journals (Sweden)

    Muzher M. Ibraheem

    2013-05-01

    Full Text Available             The aim of this research is to study the kinetic reaction models for catalytic hydrogenation of aromatic content for Basrah crude oil (BCO and vacuum gas oil (VGO derived from Kirkuk crude oil which has the boiling point rang of (611-833K.            This work is performed using a hydrodesulphurization (HDS pilot plant unit located in AL-Basil Company. A commercial (HDS catalyst cobalt-molybdenum (Co-Mo supported in alumina (γ-Al2O3 is used in this work. The feed is supplied by North Refinery Company in Baiji. The reaction temperatures range is (600-675 K over liquid hourly space velocity (LHSV range of (0.7-2hr-1 and hydrogen pressure is 3 MPa with H2/oil ratio of 300 of Basrah Crude oil (BCO, while the corresponding conditions for vacuum gas oil (VGO are (583-643 K, (1.5-3.75 hr-1, 3.5 MPa and 250  respectively .            The results showed that the reaction kinetics is of second order for both types of feed. Activation energies are found to be 30.396, 38.479 kJ/mole for Basrah Crude Oil (BCO and Vacuum Gas Oil (VGO respectively.

  11. Coal anion structure and chemistry of coal alkylation. Fourth quarterly progress report, December 1, 1977--February 28, 1978. [Carbon atoms in butyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1978-01-01

    Three research problems are in progress. First, work is progressing well concerning the methods appropriate for the reductive alkylation of Illinois No. 6 coal samples. We have investigated the influence of the leaving group on the conversion of the Illinois coal to a soluble material. We find that the n-butyl iodide is more effective than other n-butyl halides. Second, preliminary results have been obtained concerning the distribution of hydrogen and deuterium atoms in the reaction of Illinois No. 6 coal samples with perdeuteriotetralin at 400/sup 0/C. Third, the nuclear magnetic resonance spectra of appropriate model compounds with n-butyl groups have been tabulated for comparison with the spectroscopic results obtained from coal alkylation products. Fourth, the chromatographic procedures necessary for the separation of the coal samples are being developed.

  12. Method to liquefy coal

    Energy Technology Data Exchange (ETDEWEB)

    Cronauer, D.C.; Kehl, W.L.

    1977-06-08

    In a method to liquify coal in the presence of hydrogen and hydrogen-transfer solvents, a hydrogenation catalyst is used in which an amorphous aluminium phosphate is taken as catalyst carrier. The particular advantage of aluminium phosphate catalyst carriers is their property of not loosing their mechanical strength even after manifold oxidizing regeneration (burning off the deposited carbon). The quantity of carbon deposited on the catalyst when using an aluminium phosphate carrier is considerably loss than with usual catalyst carriers.

  13. The Charfuel coal refining process

    International Nuclear Information System (INIS)

    Meyer, L.G.

    1991-01-01

    The patented Charfuel coal refining process employs fluidized hydrocracking to produce char and liquid products from virtually all types of volatile-containing coals, including low rank coal and lignite. It is not gasification or liquefaction which require the addition of expensive oxygen or hydrogen or the use of extreme heat or pressure. It is not the German pyrolysis process that merely 'cooks' the coal, producing coke and tar-like liquids. Rather, the Charfuel coal refining process involves thermal hydrocracking which results in the rearrangement of hydrogen within the coal molecule to produce a slate of co-products. In the Charfuel process, pulverized coal is rapidly heated in a reducing atmosphere in the presence of internally generated process hydrogen. This hydrogen rearrangement allows refinement of various ranks of coals to produce a pipeline transportable, slurry-type, environmentally clean boiler fuel and a slate of value-added traditional fuel and chemical feedstock co-products. Using coal and oxygen as the only feedstocks, the Charfuel hydrocracking technology economically removes much of the fuel nitrogen, sulfur, and potential air toxics (such as chlorine, mercury, beryllium, etc.) from the coal, resulting in a high heating value, clean burning fuel which can increase power plant efficiency while reducing operating costs. The paper describes the process, its thermal efficiency, its use in power plants, its pipeline transport, co-products, environmental and energy benefits, and economics

  14. Report on the coal energy achievements in the Sunshine Project in fiscal 1988; 1989 nendo sunshine keikaku seika hokokusho. Sekitan energy

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1989-07-01

    This paper describes the achievements in the Sunshine Project in fiscal 1988 in studies on coal liquefaction. The liquefaction mechanisms may be conceived to work in the following three manners: radicals produced by spontaneous bond and cleavage of coal molecules draw out hydrogen from the donor and stabilize it; bond, cleavage and stabilization due to hydrogenation from the donor to coal aromatic n