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Sample records for technical methanation catalysts

  1. Discovery of technical methanation catalysts based on computational screening

    DEFF Research Database (Denmark)

    Sehested, Jens; Larsen, Kasper Emil; Kustov, Arkadii

    2007-01-01

    Methanation is a classical reaction in heterogeneous catalysis and significant effort has been put into improving the industrially preferred nickel-based catalysts. Recently, a computational screening study showed that nickel-iron alloys should be more active than the pure nickel catalyst...

  2. Catalytic reduction of SO{sub 2} with methane over molybdenum catalyst. Technical report, March 1--May 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Wiltowski, T.

    1995-12-31

    One of the primary concerns in coal utilization is the emission of sulfur compounds, especially SO{sub 2}. This project deals with catalytic reduction of SO{sub 2} with methane using molybdenum sulfide catalyst supported on different activated carbons: Darco TRS, ROZ-3, and an activated carbon prepared from Illinois coal IBC-110. The work conducted during this quarter included preparation of activated carbons from Illinois coal, preparation of the catalysts on these supports, and experiments on SO{sub 2} reduction with methane at different feed ratio SO{sub 2}: CH{sub 4}. It was found that at the feed ratio 1:1, 10% MoS{sub 2} supported on Darco TRS catalyst has highest activity at low temperatures; at higher temperatures, the catalysts 15% and 20% MoS{sub 2} supported on Darco TRS exhibit high activity in both SO{sub 2} conversion (> 90%) and yield of elemental sulfur (97.4% for 20% MoS{sub 2} at 600 C). For catalyst supported on ROZ-3, this having 10% of MOS{sub 2} showed high activity in the reaction. To determine the effect of feed ratio on the reaction, the catalysts with 15% loading of MoS{sub 2} supported on Darco TRS and ROZ-3 were used. For catalyst supported on ROZ-3 activated carbon, the effect of feed ratio is dramatic, especially at the higher temperatures at which the conversion of SO{sub 2} increases more than twice when the feed contains excess of methane. For catalyst supported on Darco TRS activated carbons, there is practically no difference in SO{sub 2} conversion for feed ratios 1:1 and 1:2 (with respect for methane).

  3. Methanization - Technical sheet

    International Nuclear Information System (INIS)

    Bastide, Guillaume

    2015-02-01

    This document explains fundamentals of methanization such as biological reactions and conditions suitable for biogas production (temperature, pH, anaerobic medium, and so on). It also proposes an overview of available techniques, of the present regulation, of environmental impacts, and of costs and profitability of methanization installations. Examples of installations are provided, as well as a set of questions and answers. Perspectives of development are finally discussed in terms of sector development potential, of regulatory evolution, of new perspectives for gas valorisation, of need of acquisition of reference data due to the relatively low number of existing installations, and of research and development

  4. Catalytic reduction of SO{sub 2} with methane over molybdenum catalyst. Quarterly technical report, September 1, 1994--November 30, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Wiltowski, T.

    1995-03-01

    One of the primary concerns in coal utilization is the emission of sulfur compounds, especially SO{sub 2}. This project deals with catalytic reduction of SO{sub 2} with methane using molybdenum sulfide catalyst supported on different activated carbons: Darco TRS, Norit ROZ-3, and an activated carbon prepared from Illinois coal IBC-110. The work conducted during this quarter has concentrated on catalyst preparation and characterization along with synthesis of activated carbon from IBC-110 coal, as well as, construction of the apparatus for catalytic tests of SO{sub 2} reduction with methane. It was found that Darco TRS supported catalysts have larger surface area than the pure activated carbon, whereas the impregnation of Norit ROZ-3 did not significantly change the BET surface area. Also, the synthesis of activated carbon support from IBC-110 is in progress.

  5. A biomimetic methane-oxidising catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Dalton, H. [Warwick Univ., Coventry (United Kingdom). Dept. of Biological Sciences

    1996-12-31

    The diminishing resources of petroleum oil has meant that there has been considerable efforts in recent years to find a suitable substitute for gasoline as a transportation fuel. Methanol has been identified as a suitable substitute since it is a readily combustible fuel which can be manufactured from a number of different sources. Methane is commonly used as a starting material for the production of synthesis gas (CO + H{sub 2}) and hence methanol. It is well known that the cleavage of the C-H bond of methane is extremely difficult (bond energy is around 104 kcal/mol) and that fairly drastic conditions are required to convert methane into methanol. Temperatures around 1200 deg C and pressures of up to 100 atmospheres over metal catalysts in a series of reactions are required to effect this process. Efforts have been made to reduce the temperature and the number of steps by using lanthanide ruthenium oxide catalyst but such reactions are still thermodynamically endothermic. An energetically more efficient reaction would be the direct conversion of methane to methanol using oxygen as the oxidant: CH{sub 4} + 1/2O{sub 2} -> CH{sub 3}OH {Delta}H deg = - 30.7 kcal/mol. Such a direct oxidation route is manifest in the bacterially-mediated oxidation of methane by methanotrophic bacteria. These organisms effect the direct oxidation of methane to methanol by the enzyme methane monooxygenase (MMO) as part of the reaction sequences to oxidize methane to carbon dioxide. (14 refs.)

  6. Coprecipitated nickel-alumina methanation catalysts

    International Nuclear Information System (INIS)

    Kruissink, E.C.

    1981-01-01

    In the last few years there has been a renewed interest in the methanation reaction CO+3H 2 =CH 4 +H 2 O. The investigations described in this thesis were performed in relation to the application of this reaction, within the framework of the so-called 'NFE' project, also called 'ADAM' and 'EVA' project. This project, which has been under investigation in West Germany for some years, aims at the investigation of the feasibility of transporting heat from a nuclear high temperature reactor by means of a chemical cycle. A promising possibility to realize such a cycle exists in applying the combination of the endothermic steam reforming of methane and the exothermic methanation reaction. This thesis describes the investigations into a certain type of methanation catalyst, viz. a coprecipitated nickel-alumina catalyst, with the aim to give more insight into the interrelationship between the preparation conditions on the one hand and catalyst properties such as activity and stability on the other hand. (Auth.)

  7. Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

    Energy Technology Data Exchange (ETDEWEB)

    Tait, Steven L. [Indiana Univ., Bloomington, IN (United States)

    2016-10-01

    serve as easily tuned model systems for exploring the chemistry of single-site transition metals and tandem catalysts that could then be developed into a zeolite or other stable support structures. In this final technical report, three major advances our described that further these goals. The first is a study demonstrating the ability to tune the oxidation state of V single-site centers on a surface by design of the surrounding ligand field. The synthesis of the single-site centers was developed in a previous reporting period of this project and this new advance shows a distinct new ability of the systems to have a designed oxidation state of the metal center. Second, we demonstrate metal complexation at surfaces using vibrational spectroscopy and also show a metal replacement reaction on Ag surfaces. Third, we demonstrate a surface-catalyzed dehydrocyclization reaction important for metal-organic catalyst design at surfaces.

  8. Supported Catalysts for CO2 Methanation: A Review

    Directory of Open Access Journals (Sweden)

    Patrizia Frontera

    2017-02-01

    Full Text Available CO2 methanation is a well-known reaction that is of interest as a capture and storage (CCS process and as a renewable energy storage system based on a power-to-gas conversion process by substitute or synthetic natural gas (SNG production. Integrating water electrolysis and CO2 methanation is a highly effective way to store energy produced by renewables sources. The conversion of electricity into methane takes place via two steps: hydrogen is produced by electrolysis and converted to methane by CO2 methanation. The effectiveness and efficiency of power-to-gas plants strongly depend on the CO2 methanation process. For this reason, research on CO2 methanation has intensified over the last 10 years. The rise of active, selective, and stable catalysts is the core of the CO2 methanation process. Novel, heterogeneous catalysts have been tested and tuned such that the CO2 methanation process increases their productivity. The present work aims to give a critical overview of CO2 methanation catalyst production and research carried out in the last 50 years. The fundamentals of reaction mechanism, catalyst deactivation, and catalyst promoters, as well as a discussion of current and future developments in CO2 methanation, are also included.

  9. Methane Steam Reforming Kinetics for a Rhodium-Based Catalyst

    DEFF Research Database (Denmark)

    Jakobsen, Jon Geest; Jakobsen, M.; Chorkendorff, Ib

    2010-01-01

    Methane steam reforming is the key reaction to produce synthesis gas and hydrogen at the industrial scale. Here the kinetics of methane steam reforming over a rhodium-based catalyst is investigated in the temperature range 500-800 A degrees C and as a function of CH4, H2O and H-2 partial pressures...

  10. CO methanation over supported bimetallic Ni-Fe catalysts: From computational studies towards catalyst optimization

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Frey, Anne Mette; Larsen, Kasper Emil

    2007-01-01

    , we report a more detailed catalytic study aimed at optimizing the catalyst performance. For this purpose, two series of mono and bimetallic Ni-Fe catalysts supported on MgAl2O4 and Al2O3, respectively, were prepared. All catalysts were tested in the CO methanation reaction in the temperature interval...

  11. Basic approach to evaluate methane partial oxidation catalysts

    CSIR Research Space (South Africa)

    Parmaliana, A

    1993-09-01

    Full Text Available . The effects of reactor diameter recycle flow, catalyst weight, and methane-to-oxygen ratios on the catalyst activity have been outlined. By performing several blank tests with an empty and a quartz-filled reactor, it has been demonstrated that the gas...

  12. Bio-methane. Challenges and technical solutions

    International Nuclear Information System (INIS)

    Blaisonneau, Laurent; Carlu, Elieta; Feuillette, Vincent

    2012-06-01

    Among the new energy sectors in development, biogas has many benefits: several valorization possibilities (bio-methane, electricity and heat), continuous production, easy storage. In Europe, and particularly in France, the bio-methane market will be in the next years a driver for the improvement of the economic, environmental and social performance of the actors of the value chain of biogas. ENEA releases a report on the current state of the bio-methane market in Europe. This publication mainly describes: An outlook of the market evolution and the corresponding stakes for the actors of this sector, the technical and economic characteristics, maturity level and specificities of each biogas upgrading process, An analysis of the French regulatory framework for bio-methane injection into the grid

  13. Small Molecule Catalysts for Harvesting Methane Gas

    Energy Technology Data Exchange (ETDEWEB)

    Baker, S. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ceron-Hernandez, M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Oakdale, J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lau, E. Y. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-12-06

    As the average temperature of the earth increases the impact of these changes are becoming apparent. One of the most dramatic changes to the environment is the melting of arctic permafrost. The disappearance of the permafrost has resulted in release of streams of methane that was trapped in remote areas as gas hydrates in ice. Additionally, the use of fracking has also increased emission of methane. Currently, the methane is either lost to the atmosphere or flared. If these streams of methane could be brought to market, this would be an abundant source of revenue. A cheap conversion of gaseous methane to a more convenient form for transport would be necessary to economical. Conversion of methane is a difficult reaction since the C-H bond is very stable (104 kcal/mole). At the industrial scale, the Fischer-Tropsch reaction can be used to convert gaseous methane to liquid methanol but is this method is impractical for these streams that have low pressures and are located in remote areas. Additionally, the Fischer-Tropsch reaction results in over oxidation of the methane leading to many products that would need to be separated.

  14. Characteristics of honeycomb catalysts to recover tritiated hydrogen and methane

    International Nuclear Information System (INIS)

    Tatsuhiko, Uda; Masahiro, Tanaka; Kenzo, Munakata

    2007-01-01

    Applicability of honeycomb catalysts to the tritium recovery system was examined considering tritium release accidents in the fusion plant where large volumes of air would be processed by the air cleanup system. Catalytic oxidation of isotopic hydrogen isotopes including tritium is a conventional method for the removal of tritium from air in the working space. However, the high throughput of air causes pressure drop in catalyst beds, which results in high load to the process gas pumping system. The honeycomb catalyst has an advantage in terms of pressure drop, which is estimated to be far less than that in conventional particle-packed catalyst beds. Our previous studies revealed that honeycomb catalysts made of cordierite and Al-Cr-Fe metal alloy substances have preferable oxidizing performance. It was found that the platinum-deposited cordierite catalyst shows the higher oxidation rate for hydrogen gas, and the palladium-deposited metal honeycomb catalyst shows the higher oxidation rate for methane gas. In this study, the properties of honeycomb catalysts were more systematically studied by changing experimental parameters such as noble metal content, mesh density and so forth to obtain design data base for high performance honeycomb catalysts. With regard to catalysts, the amount of noble metal deposited on the honeycomb substrates were varied from 1 g/L to 4 g/L and the mesh density of the honeycombs were changed from 260 to 400 CPSI as well. For operating conditions, the flow rate of the process gases was varied from 0.016 to 0.12 m 3 /hr, and the concentration of water vapor was changed from 0 to 1.4 %. Results of experimental study suggest that honeycomb catalysts are useful for the treatment of gases with high volumetric velocity in a fusion plant because of their low pressure drop in the catalyst reactor. The platinum catalysts were found to be suitable for oxidation of hydrogen gas, while the palladium catalysts exhibit better performance for oxidation of

  15. Syngas production from the reforming of methane over catalysts

    Indian Academy of Sciences (India)

    FARIS A J AL-DOGHACHI

    2017-11-11

    Nov 11, 2017 ... NixO (x= 0, 0.03, 0.07, 0.15; 1 wt% Co each), we performed the dry reforming of methane. The catalysts were prepared by K2CO3 co-precipitation from aqueous nickel nitrate hexahydrate and magnesium nitrate hexahydrate. Impregnation of cobalt(II)acetylacetonate onto MgO-NiO was then conducted.

  16. Catalytic deactivation on methane steam reforming catalysts. 2. Kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Agnelli, M.E.; Ponzi, E.N.; Yeramian, A.A.

    1987-08-01

    The kinetics of methane steam reforming reaction over an alumina-supported nickel catalyst was investigated at a temperature range of 640-740/sup 0/C in a flow reactor at atmospheric pressure. The experiments were performed varying the inlet concentration of methane, hydrogen, and water. A kinetic scheme of the Houghen-Watson type was satisfactorily proposed assuming the dissociative adsorption of CH/sub 4/ as the rate-limiting step, but this kinetic scheme can be easily replaced by a first-order kinetics (r/sub CH/4/sub / = kapparho/sub CH/4/sub /) for engineering purposes. Catalyst activation with H/sub 2/ and N/sub 2/ mixtures or with the reactant mixture results in the same extent of reaction.

  17. Dual catalyst bed concept for catalytic partial oxidation of methane to synthesis gas

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    A system with two catalyst beds instead of one single metal catalyst bed is proposed for catalytic partial oxidation of methane (CPOM) to synthesis gas. In this dual catalyst bed system, an irreducible stable oxide, such as yttrium-stabilized zirconia (YSZ), is used in the first catalyst bed to

  18. Nickel-containing catalysts for methane oxidation to synthesis gas

    Directory of Open Access Journals (Sweden)

    Kusman Dossumov

    2014-12-01

    Full Text Available The partial oxidation of methane to synthesis gas was studied on oxides of metals of variable valence (Mn, La, Cr and Ni, supported on a carrier – ɣ-Al2O3. Among the catalysts studied, the sample of 3% Ni/ɣ-Al2O3 showed the best characteristics by yields of hydrogen and carbon monoxide in the reaction of partial oxidation of methane. The optimal conditions of the process (the reaction temperature of 850 °C, the volume rate of 4500 h-1, and the ratio CH4: O2 = 2:1 cause the increase the concentration of hydrogen and carbon monoxide to 72.2 and 75.3%, respectively. The effect of the heat-treatment temperature and textural characteristics of the Ni/ ɣ-Al2O3 catalyst on its catalytic activity was studied. The NiCe/Al2O3 catalyst developed showed a high stability during 30 hours.

  19. In silico search for novel methane steam reforming catalysts

    DEFF Research Database (Denmark)

    Xu, Yue; Lausche, Adam C; Wang, Shengguang

    2013-01-01

    This paper demonstrates a method for screening transition metal and metal alloy catalysts based on their predicted rates and stabilities for a given catalytic reaction. This method involves combining reaction and activation energies (available to the public via a web-based application ‘Cat......App’) with a microkinetic modeling technique to predict the rates and selectivities of a prospective material. This paper illustrates this screening technique using the steam reforming of methane to carbon monoxide and hydrogen as a test reaction. While catalysts are already commercially available for this process......, the method demonstrated in this paper is very general and could be applied to a wide range of catalytic reactions. Following the steps outlined herein, such an analysis could potentially enable researchers to understand reaction mechanisms on a fundamental level and, on this basis, develop leads for new...

  20. Additive Manufacturing of Catalyst Substrates for Steam-Methane Reforming

    Science.gov (United States)

    Kramer, Michelle; McKelvie, Millie; Watson, Matthew

    2018-01-01

    Steam-methane reforming is a highly endothermic reaction, which is carried out at temperatures up to 1100 °C and pressures up to 3000 kPa, typically with a Ni-based catalyst distributed over a substrate of discrete alumina pellets or beads. Standard pellet geometries (spheres, hollow cylinders) limit the degree of mass transfer between gaseous reactants and catalyst. Further, heat is supplied to the exterior of the reactor wall, and heat transfer is limited due to the nature of point contacts between the reactor wall and the substrate pellets. This limits the degree to which the process can be intensified, as well as limiting the diameter of the reactor wall. Additive manufacturing now gives us the capability to design structures with tailored heat and mass transfer properties, not only within the packed bed of the reactor, but also at the interface between the reactor wall and the packed bed. In this work, the use of additive manufacturing to produce monolithic-structured catalyst substrate models, made from acrylonitrile-butadiene-styrene, with enhanced conductive heat transfer is described. By integrating the reactor wall into the catalyst substrate structure, the effective thermal conductivity increased by 34% from 0.122 to 0.164 W/(m K).

  1. Boron-containing catalysts for dry reforming of methane to synthesis gas

    KAUST Repository

    Takanabe, Kazuhiro

    2018-01-04

    The present invention uses a cobalt catalyst for carbon dioxide reforming of lower alkanes to synthesis gas having a cobalt catalyst on an oxide support where the supported cobalt catalyst has been modified with a boron precursor. The boron-treated cobalt catalyst systems as described herein show significant increases in the conversion of CH4 and CO2 during the dry reforming of methane (DRM) reaction as compared to traditional catalysts. Described herein are supported catalysts and methods of using the catalysts for the dry reforming of methane to synthesis gas, with the supported catalysts in the present invention include a boron-treated cobalt catalyst disposed on an oxide support. Also described herein are processes for preparing the supported catalysts.

  2. Pd enhanced WC catalyst to promote heterogeneous methane combustion

    International Nuclear Information System (INIS)

    Terracciano, Anthony Carmine; De Oliveira, Samuel; Siddhanti, Deepti; Blair, Richard; Vasu, Subith S.; Orlovskaya, Nina

    2017-01-01

    Highlights: • Pd enhanced WC catalyst particles were synthesized via mechanochemical alloying. • Catalyst was characterized by XRD, XRF, SEM, and EDS. • Catalyst was deposited on porous ZrO 2 and evaluated in heterogeneous combustion. • During combustion temperature profiles and spectral emissions were collected. - Abstract: The efficiency of combustion for low cost heat production could be greatly enhanced if an active and low cost catalyst would be used to facilitate the chemical reactions occurring during combustor operation. Within this work an experimental study of palladium (Pd) enhanced tungsten carbide (WC) catalyst, synthesized via high energy ball milling and deposited by dip coating onto a magnesia partially stabilized zirconia (MgO-ZrO 2 ) porous matrix of 10 ppin was evaluated in heterogeneous methane combustion. The synthesized powder was characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) coupled with Energy Dispersive Spectroscopy (EDS) analysis, as well as by X-ray Fluorescence (XRF); and the morphology of the deposited WC-Pd coating was also characterized using SEM and EDS. Performance evaluation of the heterogeneous combustor with WC-Pd coated MgO-ZrO 2 porous media was conducted at constant air flow rate and various equivalence ratios of methane/air gaseous mixtures, while monitoring axial temperature profiles within the combustion chamber using thermocouples, as well as thermal radiative and acoustic emissions from the combustor exhaust using an externally placed CCD camera and a microphone. It was found that there is a strong dependence of flame position and maximum temperature on equivalence ratio (φ) over the range of 0.47 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02. Additionally it was found that over the same equivalence ratio range, there is a characteristic 4 peak acoustic signature between 200 and 500 Hz. It was found that at higher equivalence ratios 0.51 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02 the performance of

  3. Influence of trace substances on methanation catalysts used in dynamic biogas upgrading

    DEFF Research Database (Denmark)

    Jurgensen, Lars; Ehimen, Ehiazesebhor Augustine; Born, Jens

    2015-01-01

    The aim of this work was to study the possible deactivation effects of biogas trace ammonia concentrations on methanation catalysts. It was found that small amounts of ammonia led to a slight decrease in the catalyst activity. A decrease in the catalyst deactivation by carbon formation was also o...

  4. DEVELOPMENT OF A CATALYST/SORBENT FOR METHANE REFORMING

    Energy Technology Data Exchange (ETDEWEB)

    B.H. Shanks; T.D. Wheelock; Justinus A. Satrio; Timothy Diehl; Brigitte Vollmer

    2004-09-27

    This work has led to the initial development of a very promising material that has the potential to greatly simplify hydrocarbon reforming for the production of hydrogen and to improve the overall efficiency and economics of the process. This material, which was derived from an advanced calcium-based sorbent, was composed of core-in-shell pellets such that each pellet consisted of a CaO core and an alumina-based shell. By incorporating a nickel catalyst in the shell, a combined catalyst and sorbent was prepared to facilitate the reaction of hydrocarbons with steam. It was shown that this material not only catalyzes the reactions of methane and propane with steam, it also absorbs CO{sub 2} simultaneously, and thereby separates the principal reaction products, H{sub 2} and CO{sub 2}. Furthermore, the absorption of CO{sub 2} permits the water gas shift reaction to proceed much further towards completion at temperatures where otherwise it would be limited severely by thermodynamic equilibrium. Therefore, an additional water gas shift reaction step would not be required to achieve low concentrations of CO. In a laboratory test of methane reforming at 600 C and 1 atm it was possible to produce a gaseous product containing 96 mole% H{sub 2} (dry basis) while also achieving a H{sub 2} yield of 95%. Methane reforming under these conditions without CO{sub 2} absorption provided a H{sub 2} concentration of 75 mole% and yield of 82%. Similar results were achieved in a test of propane reforming at 560 C and 1 atm which produced a product containing 96 mole% H{sub 2} while CO{sub 2} was being absorbed but which contained only 69 mole% H{sub 2} while CO{sub 2} was not being absorbed. These results were achieved with an improved catalyst support that was developed by replacing a portion of the {alpha}-alumina in the original shell material with {gamma}-alumina having a much greater surface area. This replacement had the unfortunate consequence of reducing the overall compressive

  5. DFT research of methane preliminary dissociation on aluminum catalyst

    Science.gov (United States)

    Zhang, Minhua; Yu, Yingzhe; Zhang, Yongbo

    2013-09-01

    Using the quantum chemistry calculation module based on density functional theory (DFT), the stable adsorption states of Ni4 cluster on the surface of α-Al2O3(0 0 0 1) was investigated firstly, and then the most stable adsorption configuration was selected as the representative model of supported Ni4/α-Al2O3(0 0 0 1) catalyst to investigate the catalytic performance for methane preliminary dissociation. After theoretic calculation, it was found that the methane dissociation products prefer to be adsorbed on edge sites of Ni4 cluster, the adsorption priority sequence (from large to small) for the concerned species was H > O2 > CH3 ≫ CH4 > H2. Comparing with pure Ni4 cluster without support, the chemical adsorption ability of Ni4 cluster to H2 molecule is decreased after supporting on support, which would promote the desorption of product H2, and thus increase the H2 yield. The adsorption energy of O2 molecule on Ni4/α-Al2O3(0 0 0 1) is much higher than that of other molecules such as CH4 or H2 on Ni4 cluster surface. The Osbnd O bond length on the most stable adsorption site is elongated by 0.21 Å, which would promote the activation and dissociation of O2 molecule significantly and thus might facilitate the proceeding of further reaction.

  6. Reverse microemulsion prepared Ni–Pt catalysts for methane cracking to produce COx-free hydrogen

    KAUST Repository

    Zhou, Lu

    2017-09-08

    A monodispersed 15 nm Ni9Pt1 catalyst synthesized via a reverse microemulsion method, shows a lower activation energy than both Ni and Pt catalysts during the methane cracking reaction. Thanks to the synergic effect of Ni–Pt alloy, this catalyst presents a stable H2 formation rate at 700 °C, and forms carbon nanotubes, anchoring the catalyst particles on top.

  7. Methane-induced Activation Mechanism of Fused Ferric Oxide-Alumina Catalysts during Methane Decomposition

    KAUST Repository

    Reddy Enakonda, Linga

    2016-06-27

    Activation of Fe2O3-Al2O3 with CH4 (instead of H2) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces COx-free H2. In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2O3 by CH4 proceeds in three steps: Fe2O3→Fe3O4→FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A high performance catalyst for methane conversion to methanol: graphene supported single atom Co.

    Science.gov (United States)

    Yuan, Jinyun; Zhang, Wenhua; Li, Xingxing; Yang, Jinlong

    2018-02-27

    Employing first principles calculations, we show a two-step reaction mechanism for direct methane oxidation to methanol over a single atom Co-embedded graphene (Gr) catalyst, with N 2 O as the O-donor molecule. C-H activation is the rate-limiting step. The high reaction activity and selectivity under mild conditions were predicted for this catalyst.

  9. Selective methane oxidation over promoted oxide catalysts. Topical report, September 8, 1992--September 7, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Klier, K.; Herman, R.G.

    1996-12-31

    The objective of this research was to selectively oxidize methane to C{sub 2} hydrocarbons and to oxygenates, in particular formaldehyde and methanol, in high space time yields using air at the oxidant under milder reaction conditions that heretofore employed over industrially practical oxide catalysts. The research carried out under this US DOE-METC contract was divided into the following three tasks: Task 1, maximizing selective methane oxidation to C{sub 2}{sup +} products over promoted SrO/La{sub 2}O{sub 3} catalysts; Task 2, selective methane oxidation to oxygenates; and Task 3, catalyst characterization and optimization. Principal accomplishments include the following: the 1 wt% SO{sub 4}{sup 2{minus}}/SrO/La{sub 2}O{sub 3} promoted catalyst developed here produced over 2 kg of C{sub 2} hydrocarbons/kg catalyst/hr at 550 C; V{sub 2}O{sub 5}/SiO{sub 2} catalysts have been prepared that produce up to 1.5 kg formaldehyde/kg catalyst/hr at 630 C with low CO{sub 2} selectivities; and a novel dual bed catalyst system has been designed and utilized to produce over 100 g methanol/kg catalyst/hr at 600 C with the presence of steam in the reactant mixture.

  10. Recent Advances in Supported Metal Catalysts for Syngas Production from Methane

    Directory of Open Access Journals (Sweden)

    Mohanned Mohamedali

    2018-03-01

    Full Text Available Over the past few years, great attention is paid to syngas production processes from different resources especially from abundant sources, such as methane. This review of the literature is intended for syngas production from methane through the dry reforming (DRM and the steam reforming of methane (SRM. The catalyst development for DRM and SRM represents the key factor to realize a commercial application through the utilization of more efficient catalytic systems. Due to the enormous amount of published literature in this field, the current work is mainly dedicated to the most recent achievements in the metal-oxide catalyst development for DRM and SRM in the past five years. Ni-based supported catalysts are considered the most widely used catalysts for DRM and SRM, which are commercially available; hence, this review has focused on the recent advancements achieved in Ni catalysts with special focus on the various attempts to address the catalyst deactivation challenge in both DRM and SRM applications. Furthermore, other catalytic systems, including Co-based catalysts, noble metals (Pt, Rh, Ru, and Ir, and bimetallic systems have been included in this literature review to understand the observed improvements in the catalytic activities and coke suppression property of these catalysts.

  11. Review of Novel Catalysts for Biomass Tar Cracking and Methane Reforming

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.

    2007-10-10

    A review of the literature was conducted to examine the performance of catalysts other than conventional nickel catalysts, and alkaline earth and olivine based catalysts for treating hot raw product gas from a biomass gasifier to convert methane and tars into synthesis gas. Metal catalysts other than Ni included precious metals Rh, Ru, Ir, Pt, and Pd, as well as Cu, Co, and Fe in limited testing. Nickel catalysts promoted with Rh, Zr, Mn, Mo, Ti, Ag, or Sn were also examined, as were Ni catalysts on Ce2O3, TiO2, ZrO2, SiO2, and La2O3. In general, Rh stood out as a consistently superior metal catalyst for methane reforming, tar cracking, and minimizing carbon buildup on the catalyst. Ru and Ir also showed significant improvement over Ni for methane reforming. Ceria stood out as good support material and particularly good promoter material when added in small quantities to another support material such as alumina, zirconia, or olivine. Other promising supports were lanthana, zirconia, and titania.

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

    Directory of Open Access Journals (Sweden)

    Quanrun Liu

    2017-01-01

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

  13. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    Science.gov (United States)

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

    2017-11-01

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful

  14. Transient studies of low temperature catalysts for methane conversion. Final report, [September 1992--March 1996

    Energy Technology Data Exchange (ETDEWEB)

    Wolf, E.E.

    1996-09-30

    The objective of this project is to use transient techniques to study gas surface interactions during the oxidative conversion of methane. Two groups of catalysts were studied: a double oxide of vanadium and phosphate or VPO, and double oxides of Ni, Co and Rh and lanthana. The objective of the studies involving the VPO catalyst was to understand gas-surface interactions leading to the formation of formaldehyde. In the second group of catalysts, involving metallo-oxides, the main objective was to study the gas-surface interactions that determine the selectivity to C{sub 2} hydrocarbons or synthesis gas. Transient techniques were used to study the methane-surface interactions and the role of lattice oxygen. The selection of the double oxides was made on the hypothesis that the metal oxide would provide an increase interaction with methane whereas the phosphate or lanthanide would provide the sites for oxygen adsorption. The hypothesis behind this selection of catalysts was that increasing the methane interaction with the catalysts would lower the reaction temperature and thus increase the selectivity to the desired products over the total oxidation reaction. In both groups of catalysts the role of Li as a modifier of the selectivity was also studied in detail.

  15. Microchannel Methanation Reactors Using Nanofabricated Catalysts, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Makel Engineering, Inc. (MEI) and the Pennsylvania State University (Penn State) propose to develop and demonstrate a microchannel methanation reactor based on...

  16. Microchannel Methanation Reactors Using Nanofabricated Catalysts, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Makel Engineering, Inc. (MEI) and the Pennsylvania State University (Penn State) propose to develop and demonstrate a microchannel methanation reactor based on...

  17. Ni catalysts with different promoters supported on zeolite for dry reforming of methane

    KAUST Repository

    Alotaibi, Raja

    2015-07-08

    Dry reforming of methane (DRM) is considered a high endothermic reaction with operating temperatures between 700 and 1000 °C to achieve high equilibrium conversion of CH4 and CO2 to the syngas (H2 and CO). The conventional catalysts used for DRM are Ni-based catalysts. However, many of these catalysts suffer from the short longevity due to carbon deposition. This study aims to evaluate the effect of La and Ca as promoters for Ni-based catalysts supported on two different zeolite supports, ZL (A) (BET surface area = 925 m2/g, SiO2/Al2O3 mol ratio = 5.1), and ZL (B) (BET surface area = 730 m2/g, SiO2/Al2O3 mol ratio = 12), for DRM. The physicochemical properties of the prepared catalysts were characterized with XRD, BET, TEM and TGA. These catalysts were tested for DRM in a microtubular reactor at reaction conditions of 700 °C. The catalyst activity results show that the catalysts Ni/ZL (B) and Ca-Ni/ZL (B) give the highest methane conversion (60 %) with less time on stream stability compared with promoted Ni on ZL (A). In contrast, La-containing catalysts, La-Ni/ZL (B), show more time on stream stability with minimum carbon content for the spent catalyst indicating the enhancement of the promoters to the Ni/ZL (A) and (B), but with less catalytic activity performance in terms of methane and carbon dioxide conversions due to rapid catalyst deactivation.

  18. A Review on Bimetallic Nickel-Based Catalysts for CO2Reforming of Methane.

    Science.gov (United States)

    Bian, Zhoufeng; Das, Sonali; Wai, Ming Hui; Hongmanorom, Plaifa; Kawi, Sibudjing

    2017-11-17

    In recent years, CO 2 reforming of methane (dry reforming of methane, DRM) has become an attractive research area because it converts two major greenhouse gasses into syngas (CO and H 2 ), which can be directly used as fuel or feedstock for the chemical industry. Ni-based catalysts have been extensively used for DRM because of its low cost and good activity. A major concern with Ni-based catalysts in DRM is severe carbon deposition leading to catalyst deactivation, and a lot of effort has been put into the design and synthesis of stable Ni catalysts with high carbon resistance. One effective and practical strategy is to introduce a second metal to obtain bimetallic Ni-based catalysts. The synergistic effect between Ni and the second metal has been shown to increase the carbon resistance of the catalyst significantly. In this review, a detailed discussion on the development of bimetallic Ni-based catalysts for DRM including nickel alloyed with noble metals (Pt, Ru, Ir etc.) and transition metals (Co, Fe, Cu) is presented. Special emphasis has been provided on the underlying principles that lead to synergistic effects and enhance catalyst performance. Finally, an outlook is presented for the future development of Ni-based bimetallic catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Deactivating Carbon Formation on a Ni/Al2O3 Catalyst under Methanation Conditions

    DEFF Research Database (Denmark)

    Olesen, Sine Ellemann; Andersson, Klas J.; Damsgaard, Christian Danvad

    2017-01-01

    The carbon formation causing deactivation during CO methanation was studied for a Ni/Al2O3 catalyst. Sulfur-free methanation at low temperature (573 K) for various lengths of time was followed by temperature-programmed hydrogenation (TPH) providing information on carbon types involved in the deac......The carbon formation causing deactivation during CO methanation was studied for a Ni/Al2O3 catalyst. Sulfur-free methanation at low temperature (573 K) for various lengths of time was followed by temperature-programmed hydrogenation (TPH) providing information on carbon types involved...... in the deactivation of the catalyst.Three main carbon hydrogenation peaks were evident from TPHs following methanation: ∼460, ∼650, and ∼775 K. It is suggested that the ∼460 K TPH peak was composed of two peaks: a surface carbide peak at 445–460 K, and a peak due to carbon dissolved into the nickel at 485 K based...... on CO and CH4 adsorption measurements and XRD analysis. The 650 and 775 K temperature peaks are assigned to polymerized carbon structures and the ∼775K peak was found to be the primary cause of deactivation as judged by a linear correlation between its amount and the degree of catalyst deactivation...

  20. Steam and CO2 reforming of methane over a Ru/ZrO2 catalyst

    DEFF Research Database (Denmark)

    Jakobsen, Jon Geest; Jørgensen, T.L.; Chorkendorff, Ib

    2010-01-01

    The kinetics of methane steam reforming over a Ru/ZrO2 catalyst was studied at 1.3 bar total pressure and in the temperature range 425-575 degrees C. These data were fitted by combining a reactor model with a series of kinetic models. The best fit was obtained by a model with methane dissociative...... adsorption as the rate limiting step and with CO and H adspecies partly blocking the active sites. The Ru/ZrO2 catalyst was characterized by TEM and H-2 chemisorption. By comparison of ex situ and in situ TEM, it is evident that Ru particles with diameters of...

  1. Resistance of industrial nickel-containing methanation catalysts to the poisoning by organic carbon dioxide absorbents

    Directory of Open Access Journals (Sweden)

    V. N. Efremov

    2017-09-01

    Full Text Available We report the results of studies on the influences of the organic carbon dioxide absorbent – aqueous solution of activated methyldiethanolamine (MDEA – on the physico-chemical and mechanical characteristics of nickel-alumina catalyst NIAP-07-01 (NKM-1 and cement-containing catalysts NIAP-07-07 (NKM-7, Meth-134 and Meth-135 for the hydrogenation of carbon oxide (methanation. It is established that for the nickel-alumina and nickel-cement-containing catalysts subjected to activated methyldiethanolamine (MDEA it’s possible to restore their strength and catalytic properties. In order to increase the time of operation of the methanator it is recommended to apply a new Nickel cement-containing catalyst NIAP-07-07 (NKM-7, which can be produced as tablets, rings or extrudates.

  2. Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion: Sonochemical Synthesis and Characterisation.

    Science.gov (United States)

    Jodłowski, Przemysław J; Jędrzejczyk, Roman J; Chlebda, Damian K; Dziedzicka, Anna; Kuterasiński, Łukasz; Gancarczyk, Anna; Sitarz, Maciej

    2017-07-07

    The aim of this study was to obtain nanocrystalline mixed metal-oxide-ZrO₂ catalysts via a sonochemically-induced preparation method. The effect of a stabiliser's addition on the catalyst parameters was investigated by several characterisation methods including X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The sonochemical preparation method allowed us to manufacture the catalysts with uniformly dispersed metal-oxide nanoparticles at the support surface. The catalytic activity was tested in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was higher than that of the reference catalysts prepared by the incipient wetness method without ultrasonic irradiation. The cobalt and chromium mixed zirconia catalysts revealed their high activities, which are comparable with those presented in the literature.

  3. Biological conversion of methane to chemicals and fuels: technical challenges and issues.

    Science.gov (United States)

    Hwang, In Yeub; Nguyen, Anh Duc; Nguyen, Thu Thi; Nguyen, Linh Thanh; Lee, Ok Kyung; Lee, Eun Yeol

    2018-04-01

    Methane is a promising next-generation carbon feedstock for industrial biotechnology due to its low price and huge availability. Biological conversion of methane to valuable products can mitigate methane-induced global warming as greenhouse gas. There have been challenges for the conversion of methane into various chemicals and fuels using engineered non-native hosts with synthetic methanotrophy or methanotrophs with the reconstruction of synthetic pathways for target products. Herein, we analyze the technical challenges and issues of potent methane bioconversion technology. Pros and cons of metabolic engineering of methanotrophs for methane bioconversion, and perspectives on the bioconversion of methane to chemicals and liquid fuels are discussed.

  4. Reduction of a Ni/Spinel Catalyst for Methane Reforming

    DEFF Research Database (Denmark)

    Kehres, Jan; Andreasen, Jens Wenzel; Fløystad, Jostein Bø

    2015-01-01

    microscopy (HRTEM) was performed on the fresh catalyst sample. The Ni particles in the fresh catalyst sample were observed to exhibit a Ni/NiO core/shell structure. A decrease of the Ni lattice parameter is observed during the reduction in a temperature interval from 413 – 453 K, which can be related...

  5. Syngas production by reforming of methane on perovskite catalysts ...

    Indian Academy of Sciences (India)

    T V Sagar

    catalysts has become a big question.16 Non-noble metals, mostly of group VIII, are catalytically active for CH4 reforming.7,17 Among the non-noble metals, Ni is more economically viable as a catalyst. High turnover rates, the inherent availability, low cost and remarkable long-term stability are its advantages.18 Metallic Ni ...

  6. Selective oxidation of methane to ethane and ethylene over various oxide catalysts

    NARCIS (Netherlands)

    Roos, J.A.; Bakker, A.G.; Bosch, H.; van Ommen, J.G.; Ross, J.R.H.

    1987-01-01

    Preliminary results are reported for the oxidative coupling of methane to give ethane/ethylene mixtures over a series of different catalyst formulations; the temperature range studied is 650–850°C. A comparison is made of the behaviour of lead/alumina and lithium/magnesia materials. It is found that

  7. Recent Scientific Progress on Developing Supported Ni Catalysts for Dry (CO2 Reforming of Methane

    Directory of Open Access Journals (Sweden)

    Hyun Ook Seo

    2018-03-01

    Full Text Available Two major green house gases (CO2 and CH4 can be converted into useful synthetic gas (H2 and CO during dry reforming of methane (DRM reaction, and a lot of scientific efforts has been made to develop efficient catalysts for dry reforming of methane (DRM. Noble metal-based catalysts can effectively assist DRM reaction, however they are not economically viable. Alternatively, non-noble based catalysts have been studied so far, and supported Ni catalysts have been considered as a promising candidate for DRM catalyst. Main drawback of Ni catalysts is its catalytic instability under operating conditions of DRM (>700 °C. Recently, it has been demonstrated that the appropriate choice of metal-oxide supports can address this issue since the chemical and physical of metal-oxide supports can prevent coke formation and stabilize the small Ni nanoparticles under harsh conditions of DRM operation. This mini-review covers the recent scientific findings on the development of supported Ni catalysts for DRM reaction, including the synthetic methods of supported Ni nanoparticles with high sintering resistance.

  8. Syngas production from the reforming of methane over catalysts

    Indian Academy of Sciences (India)

    FARIS A J AL-DOGHACHI

    2017-11-11

    Nov 11, 2017 ... the fixed analyzer transmission (FAT) mode for both wide and narrow scanning. ... Intensity (a.u.). Figure 1. XRD patterns of the catalysts. Figure 2. TEM image for Co/Mg0.85Ni0.15O. NiO–MgO supported by cobalt catalysts revealed MgO reflections. ... due to the loss of weight during support pre-calcination,.

  9. Tailoring Catalytic Properties of Pd/Co₃O₄ Catalysts via Structure Engineering for Methane Oxidation.

    Science.gov (United States)

    Chen, Lufei; Zhu, Yan

    2018-04-01

    The catalytic behavior of Co3O4 catalysts loaded by Pd for methane oxidation can be tailored by distinct spatial architectures and surface structures of such catalysts. Pd nanoparticles nested in Co3O4 with hexagonal-like microflakes exhibited superior catalytic activity, that is, T10 = 250 °C and T90 = 325 °C are correlated to 10% and 90% conversion of methane. Further Pd/Co3O4 microflakes catalyst can almost restore to its initial value in the absence of water when water vapor was cut off. This excellent catalysis should be attributed to its exposed more open surface, more active oxygen species and stronger redox properties.

  10. Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L.

    1997-10-01

    This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

  11. Syngas production by reforming of methane on perovskite catalysts ...

    Indian Academy of Sciences (India)

    T V Sagar

    production of chemicals like urea and salicylic acid is very limited, its transformation into fuels has attracted the attention of researchers recently.5,6 Reforming of methane with carbon dioxide to produce syngas is a. *For correspondence very attractive route to produce fuels and chemicals.7. This reaction has its importance ...

  12. Spectroscopic and XRD characterisation of zeolite catalysts active for the oxidative methylation of benzene with methane

    Science.gov (United States)

    Adebajo, Moses O.; Long, Mervyn A.; Frost, Ray L.

    2004-03-01

    The benzene methylation with methane over zeolite catalysts was previously shown in our laboratory to require the presence of oxygen. Thus, a two-step mechanism involving the intermediate formation of methanol by partial oxidation of methane followed by the methylation of benzene with methanol in the second step, was postulated. This paper now reports the results of the characterisation of the zeolite catalysts used for the oxidative benzene methylation reaction in order to provide some information about their composition, structure, properties and their behaviour before and after the reaction. The catalysts were characterised by X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), FT-IR and solid state NMR. XRD results indicate that the crystalline structures of all the ZSM-5 and H-beta catalysts remained unchanged after batch reaction of benzene with methane over the catalysts in agreement with the observation that the catalysts recovered from the reactor could be reused without loss of activity. Elemental analyses and FT-IR data show that as the level of metal ion exchange increases, the Brönsted acid concentration decreases but this metal ion exchange does not totally remove Brönsted acidity. FT-IR results further show that only a small amount of acid sites is actually necessary for a catalyst to be active since used catalysts containing highly reduced Brönsted acidity are found to be reusable without any loss of their activity. 29Si and 27Al magic angle spinning (MAS) NMR together with FT-IR spectra also show that all the active zeolites catalysts contain some extra-framework octahedral aluminium in addition to the normal tetrahedral framework aluminium. The presence of this extra-lattice aluminium does not, however, have any adverse effect on the crystallinity of the catalysts both before and after oxidative benzene methylation reaction. There appears also to be no significant dealumination

  13. Development of a Catalyst/Sorbent for Methane Reforming

    Energy Technology Data Exchange (ETDEWEB)

    B.H. Shans; T.D. Wheelock; Justinus Satrio; Karl Albrecht; Tanya Harris Janine Keeley; Ben Silva; Aaron Shell; Molly Lohry; Zachary Beversdorf

    2008-12-31

    This project led to the further development of a combined catalyst and sorbent for improving the process technology required for converting CH{sub 4} and/or CO into H{sub 2} while simultaneously separating the CO{sub 2} byproduct all in a single step. The new material is in the form of core-in-shell pellets such that each pellet consists of a CaO core surrounded by an alumina-based shell capable of supporting a Ni catalyst. The Ni is capable of catalyzing the reactions of steam with CH{sub 4} or CO to produce H{sub 2} and CO{sub 2}, whereas the CaO is capable of absorbing the CO{sub 2} as it is produced. The absorption of CO{sub 2} eliminates the reaction inhibiting effects of CO{sub 2} and provides a means for recovering the CO{sub 2} in a useful form. The present work showed that the lifecycle performance of the sorbent can be improved either by incorporating a specific amount of MgO in the material or by calcining CaO derived from limestone at 1100 C for an extended period. It also showed how to prepare a strong shell material with a large surface area required for supporting an active Ni catalyst. The method combines graded particles of {alpha}-alumina with noncrystalline alumina having a large specific surface area together with a strength promoting additive followed by controlled calcination. Two different additives produced good results: 3 {micro}m limestone and lanthanum nitrate which were converted to their respective oxides upon calcination. The oxides partially reacted with the alumina to form aluminates which probably accounted for the strength enhancing properties of the additives. The use of lanthanum made it possible to calcine the shell material at a lower temperature, which was less detrimental to the surface area, but still capable of producing a strong shell. Core-in-shell pellets made with the improved shell materials and impregnated with a Ni catalyst were used for steam reforming CH{sub 4} at different temperatures and pressures. Under all

  14. Performance of catalysts for CO removal by methanation

    Energy Technology Data Exchange (ETDEWEB)

    Oshiro, Hitoshi; Nagaya, Kiichi; Mitani, Koichi [Hitachi Zosen Corp., Osaka (Japan)

    1996-12-31

    This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns an experiment in reducing by methanation to a level below 10 ppm the CO that is contained to around 1% in reformate gas.

  15. Dynamical properties of nano-structured catalysts for methane conversion: an in situ scattering study

    DEFF Research Database (Denmark)

    Kehres, Jan

    The reactivity of catalyst particles can be radically enhanced by decreasing their size down to the nanometer range. The nanostructure of a catalyst can have an enormous and positive influence on the reaction rate, for example strong structure sensitivity was observed for methane reforming...... and ammonia synthesis, and it is therefore crucial that catalysts preserve their nanostructures under operational conditions. Fundamental understanding of the relation between the catalytic activity and the morphology of the nanoparticle, their crystallinity and crystallite size, is required to improve....../NiO particles in a fresh catalyst sample showed a Ni/NiO core shell structure. The Ni lattice parameter decreased during the reduction due to the release of stress between the Ni core and the NiO shell. Ni particles sintered during heating in hydrogen after the reduction of the NiO shell. Dry reforming...

  16. Development of Coke-tolerant Transition Metal Catalysts for Dry Reforming of Methane

    KAUST Repository

    Al-Sabban, Bedour E.

    2016-11-07

    Dry reforming of methane (DRM) is an attractive and promising process for the conversion of methane and carbon dioxide which are the most abundant carbon sources into valuable syngas. The produced syngas, which is a mixture of hydrogen and carbon monoxide, can be used as intermediates in the manufacture of numerous chemicals. To achieve high conversion, DRM reaction is operated at high temperatures (700-900 °C) that can cause major drawbacks of catalyst deactivation by carbon deposition, metal sintering or metal oxidation. Therefore, the primary goal is to develop a metal based catalyst for DRM that can completely suppress carbon formation by designing the catalyst composition. The strategy of this work was to synthesize Ni-based catalysts all of which prepared by homogeneous deposition precipitation method (HDP) to produce nanoparticles with narrow size distribution. In addition, control the reactivity of the metal by finely tuning the bimetallic composition and the reaction conditions in terms of reaction temperature and pressure. The highly endothermic dry reforming of methane proceeds via CH4 decomposition to leave surface carbon species, followed by removal of C with CO2-derived species to give CO. Tuning the reactivity of the active metal towards these reactions during DRM allows in principle the catalyst surface to remain active and clean without carbon deposition for a long-term. The initial attempt was to improve the resistance of Ni catalyst towards carbon deposition, therefore, a series of 5 wt.% bimetallic Ni9Pt1 were supported on various metal oxides (Al2O3, CeO2, and ZrO2). The addition of small amount of noble metal improved the stability of the catalyst compared to their monometallic Ni and Pt catalysts, but still high amount of carbon (> 0.1 wt.%) was formed after 24 h of the reaction. The obtained results showed that the catalytic performance, particle size and amount of deposited carbon depends on the nature of support. Among the tested

  17. Oxygen-Free Conversion of Methane to Ethylene in a Plasma-Followed-by-Catalyst (PFC) Reactor

    Science.gov (United States)

    Wang, Kangjun; Li, Xiaosong; Wang, Hui; Shi, Chuan; Xu, Yong; Zhu, Aimin

    2008-10-01

    Oxygen-free conversion of methane to ethylene was investigated in a two-stage plasma-followed-by-catalyst (PFC) reactor. In the absence of catalyst, pulsed spark discharges and pulsed corona discharges were compared for methane conversion. The results showed that methane was mainly converted to acetylene, but pulsed spark discharges exhibited distinct advantages over the pulsed corona discharges in methane conversion. Thereby, pulsed spark discharges were employed and followed by Ag-Pd/SiO2 catalyst for achieving ethylene as a target product in the PFC reactor. Using the PFC reactor, a steady single-pass ethylene yield of 57% was obtained at a rate of methane conversion of 74%.

  18. Impact of heating rate and solvent on Ni-based catalysts prepared by solution combustion method for syngas methanation

    Directory of Open Access Journals (Sweden)

    Zeng Yan

    2014-12-01

    Full Text Available Ni-Al2O3 catalysts prepared by solution combustion method for syngas methanation were enhanced by employing various heating rate and different solvent. The catalytic properties were tested in syngas methanation. The result indicates that both of heating rate and solvent remarkably affect Ni particle size, which is a key factor to the catalytic activity of Ni-Al2O3 catalysts for syngas methanation. Moreover, the relationship between Ni particle size and the production rate of methane per unit mass was correlated. The optimal Ni-Al2O3 catalyst prepared in ethanol at 2°C/min, achieves a maximum production rate of methane at the mean size of 20.8 nm.

  19. Catalytic performance of Ni/MgO catalyst in methane dry reforming

    Science.gov (United States)

    Al-Swai, Basem M.; Osman, N. B.; Abdullah, Bawadi

    2017-10-01

    Methane dry reforming to synthesis gas over nickel catalysts supported on magnesium oxide has been studied. The support was prepared via co-precipitation method using ammonia solution (20 wt% in water) as the precipitating agent. 10 wt% of Ni metal was impregnated to form Ni/MgO catalyst. The prepared catalyst was characterized by different techniques, such as XRD, BET, SEM, and TGA analysis. The effect of reaction conditions on the conversions of CH4 and CO2, selectivity of H2 and CO, and carbon deposition were investigated in a tabular furnace reactor. The catalyst afforded as high as 93% CH4 conversion at 900 °C. The catalyst has also shown excellent stability during reaction at relatively higher space velocity (1.8×104 ml g-1 h-1) and 800 °C reaction temperature. TGA characterization of spent catalyst has shown lesser magnitude of carbon deposition on the surface of the catalyst at 900 °C.

  20. A review of dry (CO2) reforming of methane over noble metal catalysts.

    Science.gov (United States)

    Pakhare, Devendra; Spivey, James

    2014-11-21

    Dry (CO2) reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer-Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800-1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The most widely used catalysts for DRM are based on Ni. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. This review will cover DRM literature for catalysts based on Rh, Ru, Pt, and Pd metals. This includes the effect of these noble metals on the kinetics, mechanism and deactivation of these catalysts.

  1. Methane Sulphonic Acid is Green Catalyst in Organic Synthesis

    OpenAIRE

    Pramod Kulkarni

    2015-01-01

    Methane sulphonic acid is an alkanesulphonic acid and its chemical formula is CH3SO3H. MSA is a strong acid having pKa= 1.9 and completely ionized in 0.1 M in an aqueous solution and has small affinity to oxidize organic compounds, less corrosive and toxic than other mineral acids. MSA is also biodegradable and not evolve toxic gases. Therefore MSA is considered as green acid. Therefore its use in organic synthesis attracts many chemists to use in organic synthesis. In this review we describe...

  2. Enhanced activity and stability of La-doped CeO2 monolithic catalysts for lean-oxygen methane combustion.

    Science.gov (United States)

    Zhu, Wenjun; Jin, Jianhui; Chen, Xiao; Li, Chuang; Wang, Tonghua; Tsang, Chi-Wing; Liang, Changhai

    2018-02-01

    Effective utilization of coal bed methane is very significant for energy utilization and environment protection. Catalytic combustion of methane is a promising way to eliminate trace amounts of oxygen in the coal bed methane and the key to this technology is the development of high-efficiency catalysts. Herein, we report a series of Ce 1-x La x O 2-δ (x = 0-0.8) monolithic catalysts for the catalytic combustion of methane, which are prepared by citric acid method. The structural characterization shows that the substitution of La enhance the oxygen vacancy concentration and reducibility of the supports and promote the migration of the surface oxygen, as a result improve the catalytic activity of CeO 2 . M-Ce 0.8 La 0.2 O 2-δ (monolithic catalyst, Ce 0.8 La 0.2 O 2-δ coated on cordierite honeycomb) exhibits outstanding activity for methane combustion, and the temperature for 10 and 90% methane conversion are 495 and 580 °C, respectively. Additionally, Ce 0.8 La 0.2 O 2-δ monolithic catalyst presents excellent stability at high temperature. These Ce 1-x La x O 2-δ monolithic materials with a small amount of La incorporation therefore show promises as highly efficient solid solution catalysts for lean-oxygen methane combustion. Graphical abstract ᅟ.

  3. Potassium/calcium/nickel oxide catalysts for the oxidative coupling of methane

    NARCIS (Netherlands)

    Dooley, K.; Dooley, Kerry M.; Ross, J.R.H.; Ross, Julian R.H.

    1992-01-01

    A series of potassium/calcium/nickel oxides were tested for the oxidative coupling of methane (OCM) at 843–943 K and water addition to the feed at 0–66 mol-%. The K/Ni ratios varied from 0.0–0.6 and Ca/Ni from 0.0–11; catalysts with no nickel were also tested. At least 10% water in the feed and

  4. Methane decomposition over high-loaded Ni-Cu-SiO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jiamao; Zhao, Linjie; He, Jianchao; Dong, Liang; Xiong, Liangping; Du, Yang; Yang, Yong; Wang, Heyi, E-mail: hywang@caep.cn; Peng, Shuming, E-mail: pengshuming@caep.cn

    2016-12-15

    Graphical abstract: Methane decomposition-regeneration with air cycles over 65%Ni-20%Cu-10%SiO{sub 2} catalysts. - Highlights: • Methane decomposition over Ni-Cu-SiO{sub 2} was studied. • The deactivated catalysts were regenerated by air. • Introduction of Cu could enhance the catalytic performance of Ni-SiO{sub 2}. • The increase of the Ni-Cu particle influences the performance of the catalysts. - Abstract: The performance of Ni-SiO{sub 2} and Ni-Cu-SiO{sub 2} during repeated catalytic decomposition of methane (CDM) reactions and subsequent regeneration of the deactivated catalysts with air has been studied. The catalytic activity of the 75%Ni-25%SiO{sub 2} catalyst in the second and third CDM was lower than that during the first, while the lifetime of the catalyst did not change significantly. Both the lifetime and the catalytic activity of 65%Ni-10%Cu-25%SiO{sub 2} in the second and third CDM reactions decreased significantly. 55%Ni-20%Cu-25%SiO{sub 2} showed better performance than the other two catalysts, and its activity and lifetime did not change significantly until the third CDM reaction. The hydrogen yields of 55%Ni-20%Cu-25%SiO{sub 2} were 56.8 gH{sub 2}/gcat., 42.8 gH{sub 2}/gcat., and 2.4 gH{sub 2}/gcat. for the first, second, and third CDM reactions, respectively. Spherical carbon structures were observed on the catalysts following all three CDM reactions over 75%Ni-25%SiO{sub 2}. However, similar carbon structures were only observed following the second and third CDM over 65%Ni-10%Cu-25%SiO{sub 2}, and only following the third cycle with 55%Ni-20%Cu-25%SiO{sub 2}. The formation of spherical carbon during the repeated CDM reactions strongly influenced the performance of the catalysts.

  5. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L. [Colorado School of Mines, Golden, CO (United States)

    1995-12-31

    The United States has vast natural gas reserves which could contribute significantly to our energy security if economical technologies for conversion to liquid fuels and chemicals were developed. Many of these reserves are small scale or in remote locations and of little value unless they can be transported to consumers. Transportation is economically performed via pipeline, but this route is usually unavailable in remote locations. Another option is to convert the methane in the gas to liquid hydrocarbons, such as methanol, which can easily and economically be transported by truck. Therefore, the conversion of methane to liquid hydrocarbons has the potential to decrease our dependence upon oil imports by opening new markets for natural gas and increasing its use in the transportation and chemical sectors of the economy. In this project, we are attempting to develop, and explore new catalysts capable of direct oxidation of methane to methanol. The specific objectives of this work are discussed.

  6. Iron ore catalysts for methane decomposition to make CO x free hydrogen and carbon nano material

    KAUST Repository

    Zhou, Lu

    2018-03-27

    In this work, for the first time, iron ores with 91.7%–96.2% FeO, 1.3%–2.3% AlO, 1.2%–4.5% SiO, 1.3%–3.9% NaO, were studied directly as bulk catalysts for methane decomposition. By hydrogen pre-reduction at 850 °C, FeO species on iron ores were gradually reduced into FeO, FeO and then finally into Fe species. After reduction of 1.6 g of iron ore catalysts of 50 µm particle size with 100 mL/min pure H for 3.5 h at 850 °C, CMD life testing was conducted at 850 °C and GHSV of 3.75 L/g h and the catalyst showed a stable methane conversion for 5 h. When methane decomposition proceeded on Fe sites, FeC species would be formed to deposit graphite around themselves to finally form carbon nano onions. This carbon nano onions material showed excellent application for wastewater purification. All samples were fully characterized with XRF, XRD, H-TPR, TEM and Raman.

  7. Green chemistry perspectives of methane conversion via oxidative methylation of aromatics over zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Adebajo, M.O. [University of Queensland, St Lucia, Qld. (Australia)

    2007-06-15

    This paper provides a general overview of the recent work that we and other researchers have done on the utilisation of methane for catalytic methylation of aromatic compounds and for direct coal liquefaction for the production of liquid hydrocarbons. In particular, the paper presents a detailed description of more recent substantial experimental evidence that we have provided for the requirement of oxygen as a stoichiometry reactant for benzene methylation with methane over moderately acidic zeolite catalysts. The reaction, which has been termed 'oxidative methylation', was thus postulated to involve a two-step mechanism involving intermediate methanol formation by methane partial oxidation, followed by benzene methylation with methanol in the second step. However, strongly acidic zeolites can cause cracking of benzene to yield methylated products in the absence of oxygen. The participation of methane and oxygen, and the effective use of zeolite catalysts in this methylation reaction definitely have some positive green chemistry implications. Thus, the results of these previous studies are also discussed in this review in light of the principles and tools of green chemistry. Various metrics were used to evaluate the greenness, cost-effectiveness, and material and energy efficiency of the oxidative methylation reaction.

  8. The oxidative coupling of methane and the oxidative dehydrogenation of ethane over a niobium promoted lithium doped magnesium oxide catalyst

    NARCIS (Netherlands)

    Swaan, H.M.; Swaan, H.M.; Li, X.; Seshan, Kulathuiyer; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

    1993-01-01

    The promoting effect of niobium in a Li/MgO catalyst for the oxidative coupling of methane (OCM) and for the oxidative dehydrogenation of ethane (ODHE) has been studied in some detail. It has been found that a Li/Nb/MgO catalyst with 16 wt % niobium showed the highest activity for the C2 production

  9. Intrinsic kinetics of the oxidation of methane over an industrial copper II oxide catalyst on a gamma-alumina support

    NARCIS (Netherlands)

    Veldsink, J.W.; Veldsink, J.W.; Versteeg, Geert; van Swaaij, Willibrordus Petrus Maria

    1995-01-01

    The kinetic rate of the heterogeneously catalysed methane oxidation reaction was studied at temperatures ranging from 723 to 923 K and atmospheric pressure. A commercially available CuO catalyst supported by thermally stable γ-Al2O3 was used as the catalyst. This kinetic study was carried out in

  10. Hydrogen production by dry reforming of methane with carbon dioxide in one-dimensional nickel-based catalysts

    International Nuclear Information System (INIS)

    Lopez U, A. C.

    2016-01-01

    The main objective of this thesis is development of nickel catalysts supported over 1D matrix of cerium oxide, to be used in dry reforming methane reaction with carbon dioxide for hydrogen production. The catalysts were characterized by: Temperature Programmed Reduction (TPR), Scanning Electronic Microscopy (Sem), Surface Area (Bet method) an X Ray Diffraction (XRD). The TPR technique allowed to define reduction temperature of the active phase in the catalyst, Sem technique showed that the CeO 2 matrix had a nano rod morphology. XRD allowed to identify the crystalline phases of the catalysts. Finally, the catalysts were tested in the dry reforming methane reaction, high catalytic activity and hydrogen production were performed at 700 degrees Celsius and the catalyst with 30 wt.% of nickel. (Author)

  11. Ce - promoted catalyst from hydrotalcites for CO2 reforming of methane: calcination temperature effect

    Directory of Open Access Journals (Sweden)

    Carlos Enrique Daza

    2012-01-01

    Full Text Available Ce-promoted Ni-catalysts from hydrotalcites were obtained. The effect of calcination temperature on the chemical and physical properties of the catalysts was studied. Several techniques were used to determine the chemical and physical characteristics of oxides. The apparent activation energies of reduction were determined. Catalytic experiments at 48 L g-1h-1 without pre-reduction in CO2 reforming of methane were performed. The spinel-like phase in these oxides was only formed at 1000 ºC. The reduction of Ni2+ in the oxides was clearly affected by the calcination temperature which was correlated with catalytic performance. The catalyst calcined at 700 ºC showed the greatest activity.

  12. Dry reforming of methane in the presence of ruthenium-based catalysts

    International Nuclear Information System (INIS)

    Safariamin, M.; Tidahy, L.H.; Abi-Aad, E.; Siffert, St.; Aboukais, A.

    2009-01-01

    The catalytic activities of ruthenium-based catalysts (5 wt% Ru) supported on alumina, ceria and ceria/alumina with different proportions of ceria (nCe 10 Al, n = 1, 3, 5; n = atomic ratio) were studied for the methane reforming reaction with CO 2 (CH 4 / CO 2 = 1) in the temperature range of 400-800 C. Evaluation of coke deposited after the reaction showed carbon deposition on Ru catalysts supported on CeO 2 , 1Ce 10 Al and 3Ce 10 Al, but not on Ru/Al 2 O 3 and Ru/5Ce 10 Al. Moreover, the sample Ru/5Ce 10 Al exhibited a higher activity than the other catalysts. (authors)

  13. Synergetic effects leading to coke-resistant NiCo bimetallic catalysts for dry reforming of methane

    KAUST Repository

    Li, Lidong

    2015-01-08

    A new dry reforming of methane catalyst comprised of NiCo bimetallic nanoparticles and a Mgx(Al)O support that exhibits high coke resistance and long-term on-stream stability is reported. The structural characterization by XRD, TEM, temperature-programmed reduction, and BET analysis demonstrates that the excellent performance of this catalyst is ascribed to the synergy of various parameters, including metal-nanoparticle size, metal-support interaction, catalyst structure, ensemble size, and alloy effects.

  14. Visible-light-driven methane formation from CO2 with a molecular iron catalyst.

    Science.gov (United States)

    Rao, Heng; Schmidt, Luciana C; Bonin, Julien; Robert, Marc

    2017-08-03

    Converting CO 2 into fuel or chemical feedstock compounds could in principle reduce fossil fuel consumption and climate-changing CO 2 emissions. One strategy aims for electrochemical conversions powered by electricity from renewable sources, but photochemical approaches driven by sunlight are also conceivable. A considerable challenge in both approaches is the development of efficient and selective catalysts, ideally based on cheap and Earth-abundant elements rather than expensive precious metals. Of the molecular photo- and electrocatalysts reported, only a few catalysts are stable and selective for CO 2 reduction; moreover, these catalysts produce primarily CO or HCOOH, and catalysts capable of generating even low to moderate yields of highly reduced hydrocarbons remain rare. Here we show that an iron tetraphenylporphyrin complex functionalized with trimethylammonio groups, which is the most efficient and selective molecular electro- catalyst for converting CO 2 to CO known, can also catalyse the eight-electron reduction of CO 2 to methane upon visible light irradiation at ambient temperature and pressure. We find that the catalytic system, operated in an acetonitrile solution containing a photosensitizer and sacrificial electron donor, operates stably over several days. CO is the main product of the direct CO 2 photoreduction reaction, but a two-pot procedure that first reduces CO 2 and then reduces CO generates methane with a selectivity of up to 82 per cent and a quantum yield (light-to-product efficiency) of 0.18 per cent. However, we anticipate that the operating principles of our system may aid the development of other molecular catalysts for the production of solar fuels from CO 2 under mild conditions.

  15. Visible-light-driven methane formation from CO2 with a molecular iron catalyst

    Science.gov (United States)

    Rao, Heng; Schmidt, Luciana C.; Bonin, Julien; Robert, Marc

    2017-08-01

    Converting CO2 into fuel or chemical feedstock compounds could in principle reduce fossil fuel consumption and climate-changing CO2 emissions. One strategy aims for electrochemical conversions powered by electricity from renewable sources, but photochemical approaches driven by sunlight are also conceivable. A considerable challenge in both approaches is the development of efficient and selective catalysts, ideally based on cheap and Earth-abundant elements rather than expensive precious metals. Of the molecular photo- and electrocatalysts reported, only a few catalysts are stable and selective for CO2 reduction; moreover, these catalysts produce primarily CO or HCOOH, and catalysts capable of generating even low to moderate yields of highly reduced hydrocarbons remain rare. Here we show that an iron tetraphenylporphyrin complex functionalized with trimethylammonio groups, which is the most efficient and selective molecular electro- catalyst for converting CO2 to CO known, can also catalyse the eight-electron reduction of CO2 to methane upon visible light irradiation at ambient temperature and pressure. We find that the catalytic system, operated in an acetonitrile solution containing a photosensitizer and sacrificial electron donor, operates stably over several days. CO is the main product of the direct CO2 photoreduction reaction, but a two-pot procedure that first reduces CO2 and then reduces CO generates methane with a selectivity of up to 82 per cent and a quantum yield (light-to-product efficiency) of 0.18 per cent. However, we anticipate that the operating principles of our system may aid the development of other molecular catalysts for the production of solar fuels from CO2 under mild conditions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-28

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

  17. Solvothermal conversion of technical lignins over NiMo catalysts

    DEFF Research Database (Denmark)

    Ghafarnejad Parto, Soheila; Christensen, Jakob Munkholt; Pedersen, Lars Saaby

    of the range of available technical lignins. In this work, catalytic conversion of different types of lignin using an alumina supported NiMo catalyst (provided by Haldor Topsøe A/S) is conducted in ethanol at 310 ˚C with initial hydrogen pressure of 25 barg. The reaction time was set to 3 hours. Proton...... lignin, a renewable source of valuable chemicals would be available and the economic viabilities of the relevant industries will be promoted. Most of the recent publications have targeted one type of lignin such as Kraft lignin 1. However, it is desirable to introduce a method suitable for conversion......-Lignosulfonate (H-LS, provided by Borregaard A/S in form of Sodium-Lignosulfonate), Kraft lignin, Protobind 1000 and Organosolv lignin are among the selected lignin types. Non-catalytic conversion of each type of lignin was also performed at similar reaction conditions for comparison. The catalyst: lignin: solvent...

  18. Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

    Science.gov (United States)

    Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

    2018-03-01

    Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

  19. CO{sub 2} REFORMING OF METHANE TO SYNGAS OVER HYDROTALCITES DERRIVED CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Z. Abdelssadek; F. Touahra; A. Saadi; O. Cherifi; D. Halliche [Laboratoire de Chimie du Gaz Naturel, Faculte de Chimie, El-Alia, Alger (Algeria); K. Bachari [Centre de recherches scientifiques et techniques en analyses physico-chimiques, Alger (Algeria)

    2008-09-30

    Considerable attention has been paid to the catalytic reforming of CH4 with CO2 to synthesis gas (CH4 + CO2 - 2CO + 2H2 ) in recent years. This reaction has very important environmental implications since both CH4 and CO2 contribute to the green house effect. They are also two of the most important abundant carbon-containing materials. Therefore, converting these two gases into a valuable synthesis gas may not only reduce atmospheric emissions of CO2 and CH4 , but also satisfy the requirement of many synthesis processes. In addition, the synthesis gas produced by this reaction has a high CO content, it is more suitable for the synthesis of valuable oxygenated chemicals then that produced by conventional steam reforming. Great efforts have been focused on the development of catalysts which show high activity and stability. Layered double hydroxides (LDH), are a class of synthetic two-dimensional nanostructured anionic clays catalysts. The catalysts obtained are characterized by ICP method, DRX, FTIR and BET methods. The data obtained from chemical analysis of the calcined catalysts confirmed that the n (M2+) / n(M3+) ratio is close to the intended value of 2. Room temperature FT-IR spectra were recorded in the range 4000 - 400 cm-1 , on a Perkin Elmer spectrometer. Catalysts stability were carried out at 650 C and a 1:1 CO2 / CH4 feed ratio. It was found that performances of catalysts after 6 h in reaction indicates that within this period nor or little deactivation takes place over them: At 650 C, the NiMgAL-HDL, NiMgLa-LDH catalysts reach respectively 54.0%, 69.0%, of methane conversion versus 75.0% 79.3% respectively of CO2 conversion. However, Co- catalysts did not show any catalytic activity in these experiments conditions.

  20. Nickel/alumina catalysts modified by basic oxides for the production of synthesis gas by methane partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Requies, J.; Cabrero, M.A.; Barrio, V.L.; Cambra, J.F.; Gueemez, M.B.; Arias, P.L. [School of Engineering (UPV/EHU), Department of Chemical and Environmental Engineering, 48013 Bilbao (Spain); La Parola, V.; Pena, M.A.; Fierro, J.L.G. [Institute of Catalysis and Petrochemistry, CSIC, Cantoblanco, 28049 Madrid (Spain)

    2006-08-15

    In the present work, Ni/{alpha}-Al{sub 2}O{sub 3} catalysts modified with different amounts of CaO and MgO were used for the production of hydrogen by catalytic partial oxidation (CPO) and wet-CPO processes of methane. In the wet-CPO process, small additions of water were introduced into the feed of the reactor to improve both the H{sub 2} yield and methane conversion. The addition of water is also beneficial because coke formation becomes thermodynamically unfavorable. The catalysts were characterized before and after the reaction with XRD, XPS, TPR and TPO techniques. Several methane decomposition tests and methane pulse experiments were carried out with a view to correlating the ability of metal sites to activate methane in the absence of oxygen with the performance for CPO and wet-CPO reactions. (author)

  1. Glow Discharge Plasma-Assisted Preparation of Nickel-Based Catalyst for Carbon Dioxide Reforming of Methane

    Science.gov (United States)

    Guo, Fang; Chu, Wei; Xu, Jun-qiang; Zhong, Lin

    2008-10-01

    A plasma-assisted method was employed to prepare Ni/γ-Al2O3 catalyst for carbon dioxide reforming of methane reaction. The novel catalyst possessed higher activity and better coke-suppression performance than those of the conventional calcination catalyst. To achieve the same CH4 conversion, the conventional catalyst needed higher reaction temperature, about 50°C higher than that of the N2 plasma-treated catalyst. After the evaluation test, the deactivation rate of the novel catalyst was 1.7%, compared with 15.2% for the conventional catalyst. Different from the characterization results of the calcined catalyst, a smaller average pore diameter and a higher specific surface area were obtained for the plasma-treated catalyst. The variations of the reduction peak temperatures and areas indicated that the catalyst reducibility was promoted by plasma assistance. The dispersion of nickel was also remarkably improved, which was helpful for controlling the ensemble size of metal atoms on the catalyst surface. The modification effect of plasma-assisted preparation on the surface property of alumina supported catalyst was speculated to account for the concentration increase of absorbed CO2. An enhancement of CO2 adsorption was propitious to the inhibition of carbon formation. The coke amount deposited on plasma treated catalyst was much smaller than that on the conventional catalyst.

  2. Dry re-forming of methane to synthesis gas over lignite semicokes catalyst at high pressure

    Directory of Open Access Journals (Sweden)

    Fengbo Guo

    2016-11-01

    Full Text Available Dry re-forming of methane has been carried out in a high temperature–pressure reactor at different pressures, using Hongce lignite semicokes catalyst. The results show that CH4 and CO2 conversions are decreased as the reaction pressure increased, but both of them kept basically stable when the reaction pressure is between 0.3 and 1 MPa. The comparison shows that the effects of the temperature and the flow of reactant gas on dry re-forming of methane are consistent with between high pressure and atmospheric pressure. The ratio of CO/H2 decreased as the ratio of CH4/CO2 increased, yet the value of CO/H2 is always more than 1 at different pressures. Hongce lignite semicokes catalyst is characterized by FTIR, XRD, SEM and BET, and the analysis results reveled that the physical specific adsorption peak of CO2 at 2350 cm−1 is strengthened significantly at different pressures, the micropore area and volume of Hongce lignite semicokes reduced form 40.2 m2  g−1 and 0.019 cm3  g−1 to 34.9 m2  g−1 and 0.017 cm3  g−1, respectively. Hongce lignite semicokes catalyst exhibited better activity and stability within 0.3–1 MPa range.

  3. Investigation on the light alkanes aromatization over Zn and Ga modified HZSM-5 catalysts in the presence of methane

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qingyin; Zhang, Fengqi; Jarvis, Jack; He, Peng; Yung, Matthew M.; Wang, Aiguo; Zhao, Kai; Song, Hua

    2018-05-01

    The catalytic co-aromatization of methane and paraffin-rich raffinate oil was investigated along with hexane, heptane and octane as its model compounds over zinc and gallium modified ZSM-5 zeolite catalysts. The benzene, toluene and xylene (BTX) components derived from light alkane aromatization were highly promoted with the assistance of methane. The co-existence of Zn and Ga metal species has a positive effect on the formation of BTX components, whereas the individual metal loaded catalyst resulted in the production of heavy aromatics, suggesting that zinc and gallium have a synergistic effect on the formation of BTX under the methane environment. When concerned with gaseous analysis, the introduced methane might interact with smaller intermediates and then transform into larger hydrocarbons. From the DRIFT observation, it was witnessed that the interaction between light alkane and methane occurred on the surface of the charged Zn-Ga/ZSM-5 catalyst. According to the comprehensive catalyst characterizations, the excellent catalytic performance may be closely associated with greatly dispersed metal species on the zeolite support, improved microporous characteristic, moderate Bronsted and increased Lewis acidic sites during the paraffin-rich liquid feedstock aromatization under methane environment. This research provides a promising pathway for the highly effective and profitable utilization of petrochemical resources and natural gas.

  4. Partial oxidation of methane to methanol over catalyst ZSM-5 from coal fly ash and rice husk ash

    Directory of Open Access Journals (Sweden)

    Mirda Yanti Fusia

    2017-01-01

    Full Text Available Methane is one of the greenhouse gases that can be converted into liquid fuels such as methanol to retain most of the energy of methane and produce a cleaner environment. The conversion of methane to methanol using ZMS-5 represents a breakthrough in the utilization of methane. However, material sources for zeolite synthesis as catalyst usually are pro-analysis grade materials, which are expensive. Therefore, in this research, coal fly ash and rice husk ash were used as raw materials for mesoporous ZSM-5 zeolite synthesis. First, coal fly ash and rice husk were subjected to pre-treatment to extract silicate (SiO44− and aluminate (AlO45− and impurities separation. The ZSM-5 zeolite was synthesized through hydrothermal treatment using two types of templates. After ZSM-5 was synthesized, it was modified with Cobalt through impregnation method. The catalytic activity of both ZSM-5 and Co/ZSM-5 zeolites as heterogeneous catalysts in partial oxidation of methane were preliminary tested and compared with that commercial one. The result showed that the zeolite catalyst ZSM-5 from fly ash coal and rice husk ash has the potential to be used as catalysts in the partial oxidation of methane to methanol.

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

    Directory of Open Access Journals (Sweden)

    Irene Lock Sow Mei

    2016-08-01

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

  6. Methane dry reforming catalysts for the production of hydrogen and carbon monoxide

    International Nuclear Information System (INIS)

    Iriarte, M; Becerra, A; Castro Luna, A

    2005-01-01

    The reaction of carbon dioxide reforming of methane (dry reforming) is a very attractive way to convert low-cost reactants in synthesis gas (CO + H 2 ).Moreover, the reaction also has very important environmental effects because both methane and carbon dioxide are greenhouse gases, and may become valuable raw materials. One of the advantages of the dry reforming compared with the conventional steam reforming is the low H 2 :CO relationship in the product, which is preferred for the synthesis of oxoalcohols and oxygenated compounds. Although noble metals based catalysts have been proved to be less sensitive to coke, the high cost and restricted availability limit their use in this process.From an industrial standpoint, it is more desirable to develop nickel-based catalysts, which are resistant to carbon deposition and exhibit stable operation for extended periods of time.In this work nickel-alumina catalysts, pure or promoted with rhodium or ruthenium, were prepared using different techniques, employing aluminum and nickel alkoxides, and characterized and selected according to their catalytic activity and coking resistance.These catalysts are to be used in an inert ceramic membrane reactor.The nickel precursor is a nickel alkoxide incorporated to the matrix precursor of alumina, which at the same time is an aluminum alkoxide.Under this scheme, catalysts with a 14% nickel charge were prepared using three preparation methods: pC0: characteristics: hydrolysis and acid peptization with HNO 3 . A1C0: characteristics: thermal decomposition. A1C0H: characteristics: thermal decomposition and subsequent hydrothermal treatment.To sum up, three Ni-A1 2 O 3 catalysts, three Ni-Rh-A1 2 O 3 catalysts, and three Ni-Ru-A1 2 O 3 catalysts were prepared.Each catalyst was prepared using the three methods: pC0-Ni-X, A1C0-Ni-X, and A1C0H-Ni-X, (X= Ru or Rh).The precursors of alumina and nickel were aluminum sec-butoxide and nickel 1-methoxide-2-propoxide. Microstructure characterization

  7. High Coke-Resistance Pt/Mg1-xNixO Catalyst for Dry Reforming of Methane.

    Directory of Open Access Journals (Sweden)

    Faris A J Al-Doghachi

    Full Text Available A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50-80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions.

  8. High Coke-Resistance Pt/Mg1-xNixO Catalyst for Dry Reforming of Methane

    Science.gov (United States)

    Al-Doghachi, Faris A. J.; Islam, Aminul; Zainal, Zulkarnain; Saiman, Mohd Izham; Embong, Zaidi; Taufiq-Yap, Yun Hin

    2016-01-01

    A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50–80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions. PMID:26745623

  9. Formation of carbon nanotubes in counter-flow, oxy-methane diffusion flames without catalysts

    Science.gov (United States)

    Merchan-Merchan, Wilson; Saveliev, Alexei; Kennedy, Lawrence A.; Fridman, Alexander

    2002-03-01

    In oxygen enriched methane diffusion flames, carbon nanotubes were discovered to be formed in the region on the fuel-rich side of the flame front at an oxygen enrichment of 50%. No catalyst was employed. An opposed flow diffusion flames with varying strain rate and oxygen content in the oxidizer stream was used. Substantial quantities of nanotube material are produced at atmospheric pressure in this continuous (non-batch) process. Thermophoretic sampling of the flame and collecting the carbon material deposited near the exhaust was done. Both confirm the growth of carbon nanotubes and other carbon clusters.

  10. Structural Effect of One-Dimensional Samarium Oxide Catalysts on Oxidative Coupling of Methane.

    Science.gov (United States)

    Fu, Bo; Jiang, Tao; Zhu, Yan

    2018-05-01

    We report an interesting structural effect of one-dimensional Sm2O3 catalysts such as nanorods, nanobelts and nanotubes synthesized by a simple solvothermal method on oxidative coupling of methane. The Sm2O3 nanobelts showed the 28% CH4 conversion and 42% C2 selectivity at 500 °C. The different spatial structures and surface structures of these Sm2O3 catalysts indeed brought about the distinct exposed facets, surface active oxygen species and surface active sites, which could account for their diverse activity and products selectivity in OCM reaction. Otherwise, the Sm2O3 nanobelts doped with Sr increased the C2 selectivity to 48% at 500 °C, which enhanced the C2 yield sharply.

  11. Interfacial reactions between DBD and porous catalyst in dry methane reforming

    Science.gov (United States)

    Kameshima, Seigo; Mizukami, Ryo; Yamazaki, Takumi; Prananto, Lukman A.; Nozaki, Tomohiro

    2018-03-01

    Interaction between dielectric barrier discharge (DBD) and porous catalyst in dry methane reforming (CH4  +  CO2  =  2H2  +  2CO) was studied. Coke formation behavior and coke morphology, as well as material conversion and selectivity, over the cross-section of porous pellets was investigated comprehensively by SEM analysis, Raman spectroscopy and pulsed reforming diagnosis, showing DBD and porous pellet interaction is possible only in the interfacial region (the external surface of the pellet): neither generation of DBD nor the diffusion of plasma generated reactive species in the internal micropores is possible. Coke formation and gasification mechanism in nonthermal plasma catalysis of DMR were discussed based on the catalyst effectiveness factor: low-temperature plasma catalysis is equivalent to the high-temperature thermal catalysis.

  12. NiCo as catalyst for magnetically induced dry reforming of methane

    Science.gov (United States)

    Varsano, F.; Bellusci, M.; Provini, A.; Petrecca, M.

    2018-03-01

    In this paper we report the activation of the dry reforming reaction by induction heating of a NiCo alloy. The catalyst plays a double role, serving both as a promoter for the reforming reaction and producing the heat induced by dissipation of the electromagnetic energy. The elevated temperatures imposed by the reforming reaction suggest the choice of an alloy with a Curie temperature >800°C. In this respect Ni:Co ratio 60:40 was chosen. Alloy active sites for CH4and CO2activation are created by a mechanochemical treatment of the alloy that increases solid-state defects. The catalyst has been successfully tested in a continuous-flow reactor working under atmospheric pressure. Methane conversion and hydrogen production yields have been measured as a function of the applied magnetic field, reactant flow rate and time on stream.

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

    International Nuclear Information System (INIS)

    Makvandi, S.; Alavi, S. M.

    2011-01-01

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

  14. Fe catalysts for methane decomposition to produce hydrogen and carbon nano materials

    KAUST Repository

    Zhou, Lu

    2017-02-21

    Conducting catalytic methane decomposition over Fe catalysts is a green and economic route to produce H2 without CO/CO2 contamination. Fused 65wt% and impregnated 20wt% Fe catalysts were synthesized with different additives to investigate their activity, whereas showing Fe-Al2O3 combination as the best catalyst. Al2O3 is speculated to expose more Fe00 for the selective deposition of carbon nano tubes (CNTs). A fused Fe (65wt%)-Al2O3 sample was further investigated by means of H2-TPR, in-situ XRD, HRTEM and XAS to conclude 750°C is the optimized temperature for H2 pre-reduction and reaction to obtain a high activity. Based on density functional theory (DFT) study, a reaction mechanism over Fe catalysts was proposed to explain the formation of graphite from unstable supersaturated iron carbides decomposition. A carbon deposition model was further proposed which explains the formation of different carbon nano materials.

  15. Active and Stable Methane Oxidation Nano-Catalyst with Highly-Ionized Palladium Species Prepared by Solution Combustion Synthesis

    Directory of Open Access Journals (Sweden)

    Mahmoud M. Khader

    2018-02-01

    Full Text Available We report on the synthesis and testing of active and stable nano-catalysts for methane oxidation. The nano-catalyst was palladium/ceria supported on alumina prepared via a one-step solution-combustion synthesis (SCS method. As confirmed by X-ray photoelectron spectroscopy (XPS and high-resolution transmission electron microscopy (HTEM, SCS preparative methodology resulted in segregating both Pd and Ce on the surface of the Al2O3 support. Furthermore, HTEM showed that bigger Pd particles (5 nm and more were surrounded by CeO2, resembling a core shell structure, while smaller Pd particles (1 nm and less were not associated with CeO2. The intimate Pd-CeO2 attachment resulted in insertion of Pd ions into the ceria lattice, and associated with the reduction of Ce4+ into Ce3+ ions; consequently, the formation of oxygen vacancies. XPS showed also that Pd had three oxidation states corresponding to Pd0, Pd2+ due to PdO, and highly ionized Pd ions (Pd(2+x+ which might originate from the insertion of Pd ions into the ceria lattice. The formation of intrinsic Ce3+ ions, highly ionized (Pd2+ species inserted into the lattice of CeO2 Pd ions (Pd(2+x+ and oxygen vacancies is suggested to play a major role in the unique catalytic activity. The results indicated that the Pd-SCS nano-catalysts were exceptionally more active and stable than conventional catalysts. Under similar reaction conditions, the methane combustion rate over the SCS catalyst was ~18 times greater than that of conventional catalysts. Full methane conversions over the SCS catalysts occurred at around 400 °C but were not shown at all with conventional catalysts. In addition, contrary to the conventional catalysts, the SCS catalysts exhibited superior activity with no sign of deactivation in the temperature range between ~400 and 800 °C.

  16. Enhanced Dry Reforming of Methane on Ni and Ni-Pt Catalysts Synthesized by Atomic Layer Deposition

    Energy Technology Data Exchange (ETDEWEB)

    Gould, Troy D.; Montemore, Matthew M.; Lubers, Alia M.; Ellis, Lucas D.; Weimer, Alan; Falconer, John L.; Medlin, James W.

    2015-02-25

    Atomic layer deposition (ALD) was used to deposit Ni and Pt on alumina supports to form monometallic and bimetallic catalysts with initial particle sizes of 1–2.4 nm. The ALD catalysts were more active (per mass of metal) than catalysts prepared by incipient wetness (IW) for dry reforming of methane (DRM), and they did not form carbon whiskers during reaction due to their sufficiently small size. Catalysts modified by Pt ALD had higher rates of reaction per mass of metal and inhibited coking, whereas NiPt catalysts synthesized by IW still formed carbon whiskers. Temperature-programmed reduction of Ni catalysts modified by Pt ALD indicated the presence of bimetallic interaction. Density functional theory calculations suggested that under reaction conditions, the NiPt surfaces form Ni-terminated surfaces that are associated with higher DRM rates (due to their C and O adsorption energies, as well as the CO formation and CH4 dissociation energies).

  17. In-Situ TEM Study of a Nanoporous Ni–Co Catalyst Used for the Dry Reforming of Methane

    Directory of Open Access Journals (Sweden)

    Takeshi Fujita

    2017-10-01

    Full Text Available We performed in-situ transmission electron microscopy (TEM on a dealloyed nanoporous NiCo catalyst used for the dry reforming of methane (DRM to investigate the origin of the catalytic activity and structural durability. The in-situ observations and local chemical analysis indicated that the DRM induced chemical demixing of Ni and Co accompanied by grain refinement, implying possible “synergic effects” in a general bimetallic NiCo catalyst when used for the DRM.

  18. Template-Assisted Wet-Combustion Synthesis of Fibrous Nickel-Based Catalyst for Carbon Dioxide Methanation and Methane Steam Reforming.

    Science.gov (United States)

    Aghayan, M; Potemkin, D I; Rubio-Marcos, F; Uskov, S I; Snytnikov, P V; Hussainova, I

    2017-12-20

    Efficient capture and recycling of CO 2 enable not only prevention of global warming but also the supply of useful low-carbon fuels. The catalytic conversion of CO 2 into an organic compound is a promising recycling approach which opens new concepts and opportunities for catalytic and industrial development. Here we report about template-assisted wet-combustion synthesis of a one-dimensional nickel-based catalyst for carbon dioxide methanation and methane steam reforming. Because of a high temperature achieved in a short time during reaction and a large amount of evolved gases, the wet-combustion synthesis yields homogeneously precipitated nanoparticles of NiO with average particle size of 4 nm on alumina nanofibers covered with a NiAl 2 O 4 nanolayer. The as-synthesized core-shell structured fibers exhibit outstanding activity in steam reforming of methane and sufficient activity in carbon dioxide methanation with 100% selectivity toward methane formation. The as-synthesized catalyst shows stable operation under the reaction conditions for at least 50 h.

  19. Catalytic partial oxidation of methane over porous silica supported VO{sub x} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pirovano, C.; Schoenborn, E.; Kalevaru, V.N.; Wohlrab, S.; Luecke, B.; Martin, A. [University Rostock e.V., Rostock (Germany). Leibniz Inst. for Catalysis

    2011-07-01

    High surface area mesoporous siliceous MCM-41 and SBA-15 materials have been used as supports to disperse vanadium oxide species using wet impregnation and incipient wetness impregnation methods. These materials were used as catalysts for the partial oxidation of methane (POM) to formaldehyde. The physico-chemical properties of the solids were studied by means of BET, DR-UV/Vis spectroscopy, Py-FTIR and TEM. The influence of support and the preparation method on the dispersion of VOx is also investigated. The catalytic properties of the catalysts were examined in a fixed bed stainless steel reactor at 923 K. So far a maximum production of formaldehyde can be detected on SBA-15 supported VOx-catalysts prepared by incipient wetness impregnation. On this V/SBA-15 material a covalent attachment of catalytic active molecular vanadium species dominates, which in turn leads to a lower activation temperature and thereby reduced over-oxidation. From the best case, the space time yield of HCHO could be reached close to 775 g{sub HCHO} Kg{sub cat}{sup -1} h{sup -1}. (orig.)

  20. Decomposition of methane over alumina supported Fe and Ni–Fe bimetallic catalyst: Effect of preparation procedure and calcination temperature

    Directory of Open Access Journals (Sweden)

    A.S. Al-Fatesh

    2018-02-01

    Full Text Available Catalytic decomposition of methane has been studied extensively as the production of hydrogen and formation of carbon nanotube is proven crucial from the scientific and technological point of view. In that context, variation of catalyst preparation procedure, calcination temperature and use of promoters could significantly alter the methane conversion, hydrogen yield and morphology of carbon nanotubes formed after the reaction. In this work, Ni promoted and unpromoted Fe/Al2O3 catalysts have been prepared by impregnation, sol–gel and co-precipitation method with calcination at two different temperatures. The catalysts were characterized by X-ray diffraction (XRD, N2 physisorption, temperature programmed reduction (TPR and thermogravimetric analysis (TGA techniques. The catalytic activity was tested for methane decomposition reaction. The catalytic activity was high when calcined at 500 °C temperature irrespective of the preparation method. However while calcined at high temperature the catalyst prepared by impregnation method showed a high activity. It is found from XRD and TPR characterization that disordered iron oxides supported on alumina play an important role for dissociative chemisorptions of methane generating molecular hydrogen. The transmission electron microscope technique results of the spent catalysts showed the formation of carbon nanotube which is having length of 32–34 nm. The Fe nanoparticles are present on the tip of the carbon nanotube and nanotube grows by contraction–elongation mechanism. Among three different methodologies impregnation method was more effective to generate adequate active sites in the catalyst surface. The Ni promotion enhances the reducibility of Fe/Al2O3 oxides showing a higher catalytic activity. The catalyst is stable up to six hours on stream as observed in the activity results.

  1. Methane measurements from space: technical challenges and solutions

    Science.gov (United States)

    Riris, Haris; Numata, Kenji; Wu, Stewart; Gonzalez, Brayler; Rodriguez, Michael; Kawa, Stephan; Mao, Jianping

    2017-05-01

    We report on an airborne demonstration of atmospheric methane (CH4) measurements with an Integrated Path Differential Absorption (IPDA) lidar using an optical parametric oscillator (OPO) and optical parametric amplifier (OPA) laser transmitter and a sensitive avalanche photo detector. The lidar measures the CH4 absorption at multiple, discrete wavelengths around 1650.9 nm. In September 2015, the instrument was deployed on NASA's DC-8 airborne laboratory and measured atmospheric methane over a wide range of topography and weather conditions from altitudes of 3 km to 13 km. In this paper, we will review the results from our flights, and identify areas of improvement.

  2. Selective CO Methanation on Ru/TiO2 Catalysts: Role and Influence of Metal-Support Interactions

    DEFF Research Database (Denmark)

    Abdel-Mageed, Ali M.; Widmann, D.; Olesen, Sine Ellemann

    2015-01-01

    Aiming at a detailed understanding of the role of metal-support interactions in the selective methanation of CO in CO2-rich reformate gases, we have investigated the catalytic performance of a set of Ru/TiO2 catalysts with comparable Ru loading, Ru particle size, and TiO2 phase composition but very...

  3. Influence of deuterium on kinetics of methane isotope exchange with surface deuteroxy groups of Pt/SiO2 catalysts

    International Nuclear Information System (INIS)

    Musoyan, L.M.; Aliev, R.K.

    1990-01-01

    Reaction of isotope methane exchange with surface deuteroxy groups of 2 % Pt/SiO 2 catalyst was studied. It is shown that preliminarily chemisorbed deuterium does not decelerate the exchange reaction, but changes its mechanism. Activation energy of exchange on clean surface is equal to 25 kJ/mol; it grows in the presence of deuterium on the surface

  4. Dynamical Properties of a Ru/MgAl2O4 Catalyst during Reduction and Dry Methane Reforming

    DEFF Research Database (Denmark)

    Kehres, Jan; Jakobsen, Jon Geest; Andreasen, Jens Wenzel

    2012-01-01

    of the size regime attributed to scattering from Ru/RuO2-particles decreases slightly by about 0.2 nm during the reduction. Dry methane reforming experiments were performed in a temperature interval from 723 to 1023 K by applying a gas mixture of carbon dioxide and methane in molar ratio of 3:1. The catalyst......Combined in situ small- and wide-angle X-ray scattering (SAXS/WAXS) studies were performed in a new laboratory setup to investigate the dynamical properties of a ruthenium/spinel (Ru/MgAl2O4) catalyst, w(Ru) = 4 wt %, during the reduction and subsequent dry methane reforming. The Ru particles...... did not show any deactivation during the experiment of overall 32 h, indicated by stable turnover frequencies for methane. The mean Ru-particle diameter remained constant during the dry methane reforming experiments, revealing a high sintering stability of the Ru/MgAl2O4 catalyst....

  5. Understanding the performance and mechanism of Mg-containing oxides as support catalysts in the thermal dry reforming of methane.

    Science.gov (United States)

    Khairudin, Nor Fazila; Sukri, Mohd Farid Fahmi; Khavarian, Mehrnoush; Mohamed, Abdul Rahman

    2018-01-01

    Dry reforming of methane (DRM) is one of the more promising methods for syngas (synthetic gas) production and co-utilization of methane and carbon dioxide, which are the main greenhouse gases. Magnesium is commonly applied in a Ni-based catalyst in DRM to improve catalyst performance and inhibit carbon deposition. The aim of this review is to gain better insight into recent developments on the use of Mg as a support or promoter for DRM catalysts. Its high basicity and high thermal stability make Mg suitable for introduction into the highly endothermic reaction of DRM. The introduction of Mg as a support or promoter for Ni-based catalysts allows for good metal dispersion on the catalyst surface, which consequently facilitates high catalytic activity and low catalyst deactivation. The mechanism of DRM and carbon formation and reduction are reviewed. This work further explores how different constraints, such as the synthesis method, metal loading, pretreatment, and operating conditions, influence the dry reforming reactions and product yields. In this review, different strategies for enhancing catalytic activity and the effect of metal dispersion on Mg-containing oxide catalysts are highlighted.

  6. Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Okolie, Chukwuemeka [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Belhseine, Yasmeen F. [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Lyu, Yimeng [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA; Yung, Matthew M. [National Renewable Energy Laboratory, Golden CO 80401 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Kovarik, Libor [Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA; Stavitski, Eli [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Sievers, Carsten [School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA

    2017-09-26

    Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-07-01

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

  8. The Influence of oxide additives on Ni/Al2O3 catalysts in low temperature methane steam reforming

    International Nuclear Information System (INIS)

    Lazar, Mihaela; Dan, Monica; Mihet, Maria; Almasan, Valer

    2009-01-01

    Hydrogen is industrially produced by methane steam reforming. The process is catalytic and the usual catalyst is based on Ni as the active element. The main problem of this process is its inefficiency. It requires high temperatures at which Ni also favors the formation of graphite, which deactivates the catalysts. Ni has the advantage of being much cheaper than noble metal catalysts, so many researches are done in order to improve the properties of supported Ni catalysts and to decrease the temperature at which the process is energetically efficient. In order to obtain catalysts with high activity and stability, it is essential to maintain the dispersion of the active phase (Ni particles) and the stability of the support. Both properties can be improved by addition of a second oxide to the support. In this paper we present the results obtained in preparation and characterization of Ni/Al 2 O 3 catalysts modified by addition of CeO 2 and La 2 O 3 to alumina support. The following catalysts were prepared by impregnation method: Ni/Al 2 O 3 , Ni/CeO 2 -Al 2 O 3 and Ni/La 2 O 3 -Al 2 O 3 (10 wt.% Ni and 6 wt.% additional oxide). The catalytic surface was characterized by N 2 adsorption - desorption isotherms. The hydrogen - surface bond was characterized by Thermo-Programmed-Desorption (TPD) method. All catalysts were tested in steam reforming reaction of methane in the range of 600 - 700 deg. C, at atmospheric pressure working with CH 4 :H 2 O ratio of 1:3. The modified catalysts showed a better catalytic activity and selectivity for H 2 and CO 2 formation, at lower temperatures than the simple Ni/Al 2 O 3 catalyst. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-07-01

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

  10. A Nanomesoporous Catalyst from Modified Red Mud and Its Application for Methane Decomposition to Hydrogen Production

    Directory of Open Access Journals (Sweden)

    Xiaoke Fang

    2016-01-01

    Full Text Available A type of nanomesoporous modified red mud (MRM catalyst was prepared and utilized for catalytic methane decomposition (CMD to produce hydrogen. The modification process significantly simplified the mineral composition of the red mud (RM; in the meantime, the physical and chemical structure of RM was changed. TEM images suggested that MRM was a kind of nanomesoporous material assembled by a number of uniformly nanoscale particles, BET results showed that the pore size distributions of MRM were ranged from 3 to 12 nm, and the specific surface area and total pore volumes of red mud improved from 8.00 m2/g and 0.08 cm3/g to 190.61 m2/g and 0.39 cm3/g, respectively. The catalytic performance of the catalysts has been tested at 800°C; the results showed that MRM exhibited much higher activity and stability than RM for CMD.

  11. The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

    Science.gov (United States)

    Takano, Hiroyuki; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

    2011-07-01

    The active catalysts for methane formation from the gas mixture of CO 2 + 4H 2 with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO 2 prepared by calcination of aqueous ZrO 2 sol with Sm(NO 3) 3 and Ni(NO 3) 2. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO 2, and the activity for methanation increased by an increase in inclusion of Sm 3+ ions substituting Zr 4+ ions in the tetragonal ZrO 2 lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.

  12. Direct Synthesis of Methanol by Partial Oxidation of Methane with Oxygen over Cobalt Modified Mesoporous H-ZSM-5 Catalyst

    Directory of Open Access Journals (Sweden)

    Yuni Krisyuningsih Krisnandi

    2015-11-01

    Full Text Available Partial oxidation of methane over mesoporous catalyst cobalt modified H-ZSM-5 has been carried out. Mesoporous Na-ZSM-5 (Si/Al = 35.4 was successfully synthesized using double template method which has high surface area (450 m2/g and average pore diameter distribution of 1.9 nm. The as-synthesized Na-ZSM-5 was converted to H-ZSM-5 through multi-exchange treatment with ammonium ion solution, causing decreased crystallinity and surface area, but increased porous diameter, due to dealumination during treatment process. Moreover, H-ZSM-5 was loaded with cobalt (Co = 2.5% w by the incipient impregnation method and calcined at 550 °C. Partial oxidation of methane was performed in the batch reactor with 0.75 bar methane and 2 bar of nitrogen (with impurities of 0.5% oxygen as the input at various reaction time (30, 60 and 120 min. The reaction results show that cobalt species in catalyst has an important role, because H-ZSM-5 cannot produce methanol in partial oxidation of methane. The presence of molecular oxygen increased the percentage of methanol yield. The reaction is time-dependent with the highest methanol yield (79% was acquired using Co/H-ZSM-5 catalyst for 60 min.

  13. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  14. Selective methane chlorination to methyl chloride by zeolite Y-based catalysts

    Science.gov (United States)

    Joo, Hyeonho; Kim, Daeho; Lim, Kwang Soo; Choi, Yong Nam; Na, Kyungsu

    2018-03-01

    The CH4 chlorination over Y zeolites was investigated to produce CH3Cl in a high yield. Three different catalytic systems based on Y zeolite were tested for enhancement of CH4 conversion and CH3Cl selectivity: (i) HY zeolites in H+-form having various Si/Al ratios, (ii) Pt/HY zeolites supporting Pt metal nanoparticles, (iii) Pt/NaY zeolites in Na+-form supporting Pt metal nanoparticles. The reaction was carried out using the gas mixture of CH4 and Cl2 with the respective flow rates of 15 and 10 mL min-1 at 300-350 °C using a fixed-bed reactor under a continuous gas flow condition (gas hourly space velocity = 3000 mL g-1 h-1). Above the reaction temperature of 300 °C, the CH4 chlorination is spontaneous even in the absence of catalyst, achieving 23.6% of CH4 conversion with 73.4% of CH3Cl selectivity. Under sufficient supplement of thermal energy, Cl2 molecules can be dissociated to two chlorine radicals, which triggered the C-H bond activation of CH4 molecule and thereby various chlorinated methane products (i.e., CH3Cl, CH2Cl2, CHCl3, CCl4) could be produced. When the catalysts were used under the same reaction condition, enhancement in the CH4 conversion was observed. The Pt-free HY zeolite series with varied Si/Al ratios gave around 27% of CH4 conversion, but there was a slight decrease in CH3Cl selectivity with about 64%. Despite the difference in acidity of HY zeolites having different Si/Al ratios, no prominent effect of the Si/Al ratios on the catalytic performance was observed. This suggests that the catalytic contribution of HY zeolites under the present reaction condition is not strong enough to overcome the spontaneous CH4 chlorination. When the Pt/HY zeolite catalysts were used, the CH4 conversion reached further up to 30% but the CH3Cl selectivity decreased to 60%. Such an enhancement of CH4 conversion could be attributed to the strong catalytic activity of HY and Pt/HY zeolite catalysts. However, both catalysts induced the radical cleavage of Cl2

  15. Mn-Na{sub 2}WO{sub 4}/SiO{sub 2}. An industrial catalyst for methane coupling?

    Energy Technology Data Exchange (ETDEWEB)

    Yildiz, M.; Arndt, S.; Otremba, T.; Thomas, A.; Schomaeker, R. [Technische Univ. Berlin (Germany). Dept. of Chemistry; Simon, U.; Berthold, A.; Goerke, O.; Schubert, H. [Technische Univ. Berlin (Germany). Dept. of Materials Science; Aksu, Y. [Akdeniz Univ. (Turkey). Dept. of Material Science and Engineering

    2012-07-01

    The oxidative coupling of methane (OCM) is one of the best reactions for the direct conversion of methane. Despite all efforts, a suitable OCM process has not been put into practice yet, due to a lack of active, selective and stable catalyst. Mn-Na{sub 2}WO{sub 4}/SiO{sub 2} has attracted great interest because of its proven long term stability and its highly suitable catalytic performance. In spite of the large number of studies on this catalyst, structural characterizations are very difficult due to its complex trimetallic and multiphase nature. Previously, we studied a broad variety of support materials for the Mn-Na{sub 2}WO{sub 4}/SiO{sub 2} catalyst, e.g. Al{sub 2}O{sub 3}, TiO{sub 2}, ZrO{sub 2} and MgO. We found that SiO{sub 2} is the most suitable support material. A variation of the SiO{sub 2} materials showed that the catalytic performance does not differ substantially. However, the performance of SBA-15 supported Mn-Na{sub 2}WO{sub 4} catalyst was outstanding in comparison to all other silica supported catalysts. The reason of this substantial increase in the activity could be the ordered mesoporous structure of its support material. To understand the reaction mechanism, the kinetic isotope effect (KIE) with CD{sub 4} over Mn-Na{sub 2}WO{sub 4}/SiO{sub 2} was studied, we found that the consecutive oxidation of the C{sub 2} products is an important constraint as described in the literature for other catalysts. In order to apply this catalyst in a miniplant, we developed an upscaled preparation procedure via a fluidized bed granulation, allowing the preparation of large amounts of this catalyst. (orig.)

  16. Dry (CO2) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

    International Nuclear Information System (INIS)

    Niu, Juntian; Du, Xuesen; Ran, Jingyu; Wang, Ruirui

    2016-01-01

    Graphical abstract: - Highlights: • CH appears to be the most abundant species on Pt(1 1 1) surface in CH 4 dissociation. • CO 2 * + H* → COOH* + * → CO* + OH* is the dominant reaction pathway in CO 2 activation. • Major reaction pathway in CH oxidation: CH* + OH* → CHOH* + * → CHO* + H* → CO* + 2H*. • C* + OH* → COH* + * → CO* + H* is the dominant reaction pathway in C oxidation. - Abstract: Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H 2 /CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO 2 and CH 4 . In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH 4 direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH 4 dehydrogenation on Pt(1 1 1) surface. In the process of CO 2 activation, three possible reaction pathways are considered to contribute to the CO 2 decomposition: (I) CO 2 * + * → CO* + O*; (II) CO 2 * + H* → COOH* + * → CO* + OH*; (III) CO 2 * + H* → mono-HCOO* + * → bi-HCOO* + * [CO 2 * + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In addition, the kinetic results also indicate this process is not easy

  17. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin

    2014-03-24

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Lanthanum and cerium co-modified Ni/SiO2 catalyst for CO methanation from syngas

    Science.gov (United States)

    Gong, Dandan; Li, Shuangshuang; Guo, Shaoxia; Tang, Honggui; Wang, Hong; Liu, Yuan

    2018-03-01

    Sintering of active metal nanoparticles (NPs) and carbon deposition is critical problems for many metal catalysts, such as nickel based catalysts for generating methane from syngas. To improve the resistance to the sintering and carbon deposition, a new scheme was proposed in this work. Lanthanum and cerium co-modified Ni/SiO2 catalysts were synthesized by using perovskite type oxide of La1-xCexNiO3 loaded on SiO2 as the precursor. In a nanocrystallite of La1-xCexNiO3, ions of nickel, lanthanum and cerium are evenly mixed at atomic level and confined in the nanocrystallite, therefore, Ni NPs and the two promoters of La2O3 and CeO2 should be in close contact and highly dispersed on SiO2 after reduction. The catalysts were characterized by using XRD, TEM, BET, H2-TPD, XPS, TG and Raman techniques. Compared with the mono-promoted catalysts, the bi-promoted La0.75Ce0.25NiO3/SiO2 showed much better resistance to carbon deposition, higher resistance to sintering and higher activity for CO methanation, which are attributed to co-eliminating effect of the two promoters for the deposited carbon, confinement of the interacted two promoters for Ni NPs and the higher dispersion of Ni NPs derived from the smaller size of La0.75Ce0.25NiO3.

  19. Characterization of surface carbon formed during the conversion of methane to benzene over Mo/H-ZSM-5 catalysts

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Rosynek, Michael P.; Lunsford, Jack H.

    1998-01-01

    During the conversion of methane to benzene in the absence of oxygen over a 2 wt% Mo/H-ZSM-5 catalyst at 700 °C, three different types of surface carbon have been observed by X-ray photoelectron spectroscopy: adventitious or graphitic-like C (284.6 eV), carbidic-like C (282.7 eV), and hydrogen-poor

  20. Highly active Ni/Y-doped ZrO{sub 2} catalysts for CO{sub 2} methanation

    Energy Technology Data Exchange (ETDEWEB)

    Takano, H., E-mail: takano_hi@hitachizosen.co.jp [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Kirihata, Y.; Izumiya, K.; Kumagai, N. [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Habazaki, H., E-mail: habazaki@eng.hokudai.ac.jp [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Division of Applied Chemistry & Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Hashimoto, K. [Tohoku Institute of Technology, Sendai, 277-8515 (Japan)

    2016-12-01

    Highlights: • The Ni/Y-doped ZrO{sub 2} catalysts show highly catalytic activity for CO{sub 2} methanation. • Bidentate carbonate is a major adsorption spice on the Ni/Y-doped ZrO{sub 2} catalysts. • The oxide support of t-ZrO{sub 2} and/or c-ZrO{sub 2} with oxygen vacancies plays a key role. - Abstract: The catalytic methanation of CO{sub 2} was carried out on Ni catalysts supported on Y-doped ZrO{sub 2} with various Y{sup 3+} concentrations and Ni/(Zr + Y) molar ratio = 1. The catalysts were characterized by X-ray diffraction, scanning transmission electron microscopy, specific surface area, temperature-programmed desorption of CO{sub 2}, and temperature-programmed reaction. In addition, operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFT) was used to identify the adsorbed reaction intermediate. Catalysts supported on Y-doped ZrO{sub 2} show higher catalytic activity than the catalyst on Y-free ZrO{sub 2} with a monoclinic ZrO{sub 2} phase. The catalytic activity is also dependent upon the Y{sup 3+} concentration, and the highest activity was obtained for the catalyst with a Y/(Zr + Y) molar ratio of 0.333, which consists mainly of fcc Ni and cubic ZrO{sub 2} phase. Y{sup 3+} doping into ZrO{sub 2} introduces oxygen vacancies, which play an important role in enhancing the catalytic activity. The operando DRIFT study reveals that a CO adsorption intermediate is absent, and bidentate carbonate is an important intermediate for CH{sub 4} formation.

  1. Partial oxidation of methane to synthesis gas in a dual catalyst bed system combining irreducible oxide and metallic catalysts

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    Operation of partial oxidation of methane to synthesis gas over yttrium-stabilized zirconia (YSZ) at very high temperatures (¿900°C) slightly improves the selectivity to synthesis gas, which is caused by some activity of YSZ for steam and dry reforming of methane. LaCoO3 perovskite is not active in

  2. Statistical Analysis of Past Catalytic Data on Oxidative Methane Coupling for New Insights into the Composition of High-Performance Catalysts

    Czech Academy of Sciences Publication Activity Database

    Zavyalova, U.; Holeňa, Martin; Schlögl, R.; Baerns, M.

    2011-01-01

    Roč. 3, č. 12 (2011), s. 1935-1947 ISSN 1867-3880 Institutional research plan: CEZ:AV0Z10300504 Keywords : catalyst development * heterogeneous catalysis * methane * oxidative coupling * catalyst composition * statistical analysis Subject RIV: IN - Informatics, Computer Science Impact factor: 5.207, year: 2011

  3. Intrinsic kinetics of the oxidation of methane over an industrial copper(II) oxide catalyst on a γ-alumina support

    NARCIS (Netherlands)

    Veldsink, J.W.; Versteeg, G.F.; Swaaij, W.P.M. van

    1995-01-01

    The kinetic rate of the heterogeneously catalysed methane oxidation reaction was studied at temperatures ranging from 723 to 923 K and atmospheric pressure. A commercially available CuO catalyst supported by thermally stable γ-Al2O3 was used as the catalyst. This kinetic study was carried out in

  4. Structured Ni catalysts on porous anodic alumina membranes for methane dry reforming: NiAl 2 O 4 formation and characterization

    KAUST Repository

    Zhou, Lu

    2015-06-29

    This communication presents the successful design of a structured catalyst based on porous anodic alumina membranes for methane dry reforming. The catalyst with a strong Ni-NiAl2O4 interaction shows both excellent activity and stability. This journal is © The Royal Society of Chemistry.

  5. Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of hydrogen and nanocarbon via methane decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Guevara, J.C.; Wang, J.A.; Chen, L.F.; Valenzuela, M.A. [ESIQIE, Instituto Politecnico Nacional, Col. Zacatenco, Av. Politecnico s/n, 07738 Mexico D. F. (Mexico); Salas, P. [Centro de Fisica Aplicada y Tecnologia Avanzada, Universidad Nacional Autonoma de Mexico, Apartado Postal 1-1010, Queretaro 76000 (Mexico); Garcia-Ruiz, A. [UPIICSA, Instituto Politecnico Nacional, Te 950 Col. Granjas-Mexico, 08400 Mexico D.F. (Mexico); Toledo, J.A.; Cortes-Jacome, M.A.; Angeles-Chavez, C. [Programa de Molecular Ingenieria, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, 07730 Mexico D. F. (Mexico); Novaro, O. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, A. P. 20-364, 01000 Mexico D.F. (Mexico)

    2010-04-15

    For the first time, simultaneous production of hydrogen and nanocarbon via catalytic decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investigated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the reaction activity remained almost unchanged during 1400 min steam on time at temperatures 540, 560 and 580 C, respectively. The methane conversion level over these catalysts reached 60-75% with a 100% selectivity towards hydrogen. TEM observations revealed that most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used catalysts, keeping their exposed surface clean during the test and thus remaining active for continuous reaction without obvious deactivation. Two kinds of carbon materials, graphitic carbon (C{sub g}) as major and amorphous carbon (C{sub A}) as minor were produced in the reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nanotubes had an average diameter of approximately 30-50 nm and tens micrometers in length, depending on the reaction temperature, reaction time and Ni particle diameter. Four types of carbon nanofibers/nanotubes were detected and their formations greatly depend on the reaction temperature, time on steam and degree of the interaction between the metallic Ni and support. The respective mechanisms of the formation of nanocarbons were postulated and discussed. (author)

  6. XPS, XAES, and TG/DTA characterization of deposited carbon in methane dehydroaromatization over Ga Mo/ZSM-5 catalyst

    Science.gov (United States)

    Liu, B. S.; Jiang, L.; Sun, H.; Au, C. T.

    2007-03-01

    The catalytic dehydroaromatization of methane over 3.0%Mo/HZSM-5 and 0.1%Ga-3%Mo/HZSM-5 catalysts were reported. The nature of deposited carbon was characterized by means of XPS, XAES, TG/DTG, HRTEM, and DTA techniques. In XAES study, the type of deposited carbon was characterized based on the fine structures of d N/d E spectra. The results confirm that the sp 2/sp 3 bonding ratio of coke species increases with on-stream time, suggesting that the deposition of heavier aromatic-type carbon is the main reason for catalyst deactivation. The addition of gallium to 3.0%Mo/HZSM-5 enhances the adsorption of CO x species as well as the formation of alkene (such as ethylene). Therefore, the Ga-modified 3%Mo/HZSM-5 catalyst is more active and stable than the unmodified one.

  7. The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

    Directory of Open Access Journals (Sweden)

    Wan Azelee Wan Abu Bakar

    2015-09-01

    Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

  8. The Enhanced Catalytic Performance and Stability of Rh/γ-Al2O3 Catalyst Synthesized by Atomic Layer Deposition (ALD for Methane Dry Reforming

    Directory of Open Access Journals (Sweden)

    Yunlin Li

    2018-01-01

    Full Text Available Rh/γ-Al2O3 catalysts were synthesized by both incipient wetness impregnation (IWI and atomic layer deposition (ALD. The TEM images of the two catalysts showed that the catalyst from ALD had smaller particle size, and narrower size distribution. The surface chemical states of both catalysts were investigated by both XPS and X-ray Absorption Near Edge Structure (XANES, and the catalyst from IWI had higher concentration of Rh3+ than that from ALD. The catalytic performance of both catalysts was tested in the dry reforming of methane reaction. The catalyst from ALD showed a higher conversion and selectivity than that from IWI. The stability testing results indicated that the catalyst from ALD showed similar stability to that from IWI at 500 °C, but higher stability at 800 °C.

  9. The Enhanced Catalytic Performance and Stability of Rh/γ-Al₂O₃ Catalyst Synthesized by Atomic Layer Deposition (ALD) for Methane Dry Reforming.

    Science.gov (United States)

    Li, Yunlin; Jiang, Jing; Zhu, Chaosheng; Li, Lili; Li, Quanliang; Ding, Yongjie; Yang, Weijie

    2018-01-22

    Rh/γ-Al₂O₃ catalysts were synthesized by both incipient wetness impregnation (IWI) and atomic layer deposition (ALD). The TEM images of the two catalysts showed that the catalyst from ALD had smaller particle size, and narrower size distribution. The surface chemical states of both catalysts were investigated by both XPS and X-ray Absorption Near Edge Structure (XANES), and the catalyst from IWI had higher concentration of Rh 3+ than that from ALD. The catalytic performance of both catalysts was tested in the dry reforming of methane reaction. The catalyst from ALD showed a higher conversion and selectivity than that from IWI. The stability testing results indicated that the catalyst from ALD showed similar stability to that from IWI at 500 °C, but higher stability at 800 °C.

  10. Ceria-based model catalysts: fundamental studies on the importance of the metal-ceria interface in CO oxidation, the water-gas shift, CO2hydrogenation, and methane and alcohol reforming.

    Science.gov (United States)

    Rodriguez, José A; Grinter, David C; Liu, Zongyuan; Palomino, Robert M; Senanayake, Sanjaya D

    2017-04-03

    Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO 2 , and the production of hydrogen through the water-gas shift reaction and the reforming of methane or alcohols. Using model catalysts it has been possible to examine in detail correlations between the structural, electronic and catalytic properties of ceria-metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C-O, C-H and C-C bonds. Several studies with model ceria catalysts have shown the importance of strong metal-support interactions. In general, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.

  11. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    KAUST Repository

    Li, Lidong

    2015-02-03

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  12. Kinetics for Steam and CO2 Reforming of Methane Over Ni/La/Al2O3 Catalyst.

    Science.gov (United States)

    Park, Myung Hee; Choi, Bong Kwan; Park, Yoon Hwa; Moon, Dong Ju; Park, Nam Cook; Kim, Young Chul

    2015-07-01

    Kinetic studies of mixed (steam and dry) reforming of methane on Ni/La/Al2O3 and Ni/La-Co (1, 3 wt%)/Al2O3 catalysts were performed in an atmospheric fixed-bed reactor. Kinetic parameters for the mixed reforming over these catalysts were obtained under reaction conditions free from heat and mass transfer limitations. Variables for the mixed reforming were the reaction temperature and partial pressure of reactants. The fitting of the experimental data for the rate of methane conversion, rCH4, using the power law rate equation rCH4 = k(PrCH4)α(PCO2)β(PH2O)γ showed that the reaction orders α, β, and γ are steady and obtained values equal to α = 1, β = 0, and γ = 0. In other words, among CH4, CO2, H2O, and H2, only CH4 reaction orders were not zero and they were affected by the promoters. The apparent activation energy on catalysts Ni/La/Al2O3, Ni/La-Co (1)/Al2O3 and Ni/La-Co (3)/Al2O3 is 85.2, 93.8, and 99.4 kJ/mol, respectively. The addition of Co to Ni/La/Al2O3 was increased the apparent activation energy of the mixed reforming reaction. And the Ni/La-Co (3 wt%)/Al2O3 catalyst showed the highest reforming activity and apparent activation energy. The Co promoters can increase the apparent activation energy of mixed reforming of methane.

  13. Production of CO-rich Hydrogen Gas from Methane Dry Reforming over Co/CeO2 Catalyst

    Directory of Open Access Journals (Sweden)

    Bamidele V. Ayodele

    2016-08-01

    Full Text Available Production of CO-rich hydrogen gas from methane dry reforming was investigated over CeO2-supported Co catalyst. The catalyst was synthesized by wet impregnation and subsequently characterized by field emission scanning electron microscope (FESEM, energy dispersion X-ray spectroscopy (EDX, liquid N2 adsorption-desorption, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR and thermogravimetric analysis (TGA for the structure, surface and thermal properties. The catalytic activity test of the Co/CeO2 was investigated between 923-1023 K under reaction conditions in a stainless steel fixed bed reactor. The composition of the products (CO2 and H2 from the methane dry reforming reaction was measured by gas chromatography (GC coupled with thermal conductivity detector (TCD. The effects of feed ratios and reaction temperatures were investigated on the catalytic activity toward product selectivity, yield, and syngas ratio. Significantly, the selectivity and yield of both H2 and CO increases with feed ratio and temperature. However, the catalyst shows higher activity towards CO selectivity. The highest H2 and CO selectivity of 19.56% and 20.95% respectively were obtained at 1023 K while the highest yield of 41.98% and 38.05% were recorded for H2 and CO under the same condition. Copyright © 2016 BCREC GROUP. All rights reserved Received: 21st January 2016; Revised: 23rd February 2016; Accepted: 23rd February 2016 How to Cite: Ayodele, B.V., Khan, M.R., Cheng, C. K. (2016. Production of CO-rich Hydrogen Gas from Methane Dry Reforming over Co/CeO2 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 210-219 (doi:10.9767/bcrec.11.2.552.210-219 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.552.210-219

  14. Screening single-atom catalysts for methane activation: α -A l2O3(0001 ) -supported Ni

    Science.gov (United States)

    Gao, Fei; Gao, Shiwu; Meng, Sheng

    2017-08-01

    Methane activation is one of the biggest challenges for chemical conversion of hydrocarbons and fundamental science. We systematically screen d -block transition metal elements as potential candidates of single-atom catalysts (SACs) for methane dissociation. The adsorption of methane on free metal atoms strongly depends on the number of d electrons of SAC, where the maximum binding energy is formed with the Ni group (electronic configuration d8s2 or d9s1 ). Interestingly, the magnetic moment of the SACs decreases by 2 μB for strong interactions, suggesting that the methane-metal bond forms a spin singlet state involving two electrons of opposite spins. To examine the effect of substrates, the screened transition metals, Ni, Rh, and Pt are further put onto prototype metal oxide surfaces. The substrate dramatically modifies the discrete energy levels of a single metal and its catalytic properties. Single Ni atoms supported on an O-terminated α -A l2O3(0001 ) surface (N i1/A l2O3 ) show superior catalytic properties, with a low activation barrier of 0.4 eV (0.11 eV after zero-point energy correction) for the C-H bond dissociation and simultaneously an extreme stability with a high binding energy of ˜9.39 eV for the Ni anchor. This work identifies N i1/A l2O3 catalyst as an optimal SAC and offers new atomistic insights into the mechanism of methane activation on SACs.

  15. Evaluation of glycine excess over NiAl2O4 catalysts prepared by combustion reaction for steam methane reforming

    International Nuclear Information System (INIS)

    Leal, Elvia; Neiva, Laedna Souto; Sousa, Jean-Pierre La Martini Lima; Costa, Ana Cristina F. Melo; Gama, Lucianna; Argolo, Fabio; Andrade, Heloysa Martins Carvalho

    2009-01-01

    The aim of this work is to evaluate the catalytic activity of NiAl 2 O 4 powders, prepared by combustion reaction with different glycine contents, for the steam reforming of methane. The NiAl 2 O 4 powders were prepared according to the theory of propellants and explosives, using glycine reductant in stoichiometric ratio (Φe = 1) and in excess of 10% and 20% (Φe < 1). During the synthesis, parameters such as flame combustion temperature and time were measured. The samples were characterized by XRD, textural analysis by nitrogen adsorption (BET/BJH), TPR and evaluated as catalysts for the steam reforming of methane. The XRD results showed the presence of NiAl 2 O 4 as major phase and traces of NiO and Ni in all the samples. The glycine content increase caused a decrease of crystallite size and an increase of surface area, from 29 to 39 m 2 /g. The TPR profiles showed reduction peaks of NiO species in weak interaction with the support, and reduction of nickel present in the NiAl 2 O 4 . It was observed that higher methane conversions were obtained in the presence of NiAl 2 O 4 samples prepared using glycine excess. However, it was also observed a rapid deactivation of these catalysts due to high coke deposition onto the active surface phases. (author)

  16. In Situ Exsolution of Bimetallic Rh-Ni Nanoalloys: a Highly Efficient Catalyst for CO2Methanation.

    Science.gov (United States)

    Arandiyan, Hamidreza; Wang, Yuan; Scott, Jason; Mesgari, Sara; Dai, Hongxing; Amal, Rose

    2018-03-22

    Unique CO 2 methanation catalysts comprising bimetallic Ni-Rh nanoalloy/3DOM LaAlO 3 have been successfully prepared via a poly(methyl methacrylate) microsphere colloidal crystal-templating route, followed by the in situ growth of Ni nanoparticles (NPs). Here, we show that unlike traditional Ni particles deposited on a perovskite support, the exsolution of Ni occurs on both the external and internal surface of the porous perovskite substrate, leading to a strong metal-support interaction. Owing to the exsolution of Ni and the formation of Ni-Rh nanoalloys, a 52% enhancement in the methanation turnover frequency was obtained over the Ni-Rh/3DOM LaAlO 3 [13.9 mol/(mol h)] compared to Rh/3DOM LaNi 0.08 Al 0.92 O 3 [9.16 mol/(mol h)] before reduction treatment. The results show that the low-temperature reducibility, rich surface adsorbed oxygen species, and basic sites of the catalyst greatly improve its activity toward CO 2 methanation. The hierarchically porous structure of the perovskite support provides a high dispersion of bimetallic Ni-Rh NPs.

  17. Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane.

    Science.gov (United States)

    Zhang, Sheng; Kang, Peng; Bakir, Mohammed; Lapides, Alexander M; Dares, Christopher J; Meyer, Thomas J

    2015-12-29

    Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world's continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd-H sites and Cu-CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.

  18. De-oxygenation of CO2 by using Hydrogen, Carbon and Methane over Alumina-Supported Catalysts

    Directory of Open Access Journals (Sweden)

    R.Y. Raskar

    2012-06-01

    Full Text Available The de-oxygenation of CO2 was explored by using hydrogen, methane, carbon etc., over alumina supported catalysts. The alumina-supported ruthenium, rhodium, platinum, molybdenum, vanadium and magnesium catalysts were first reduced in hydrogen atmosphere and then used for the de-oxygenation of CO2. Furthermore, experimental variables for the de-oxygenation of CO2 were temperature (range 50 to 650 oC, H2/CO2 mole ratios (1.0 to 5, and catalyst loading (0.5 to 10 wt %. During the de-oxygenation of CO2 with H2 or CH4 or carbon, conversion of CO2, selectivity to CO and CH4 were estimated. Moreover, 25.4 % conversion of CO2 by hydrogen was observed over 1 wt% Pt/Al2O3 catalyst at 650 oC with 33.8 % selectivity to CH4. However, 8.1 to 13.9 % conversion of CO2 was observed over 1 wt% Pt/Al2O3 catalyst at 550 oC in the presence of both H2 and CH4. Moreover, 42.8 to 79.4 % CH4 was converted with 9 to 23.1 % selectivity to CO. It was observed that the de-oxygenation of CO2 by hydrogen, carbon and methane produced carbon, CO and CH4. © 2012 BCREC UNDIP. All rights reservedReceived: 6th February 2012; Revised: 23rd April 2012; Accepted: 24th April 2012[How to Cite: R. Y. Raskar, K. B. Kale, A. G. Gaikwad. (2011. De-oxygenation of CO2 by using Hydrogen, Carbon and Methane over Alumina-Supported Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 59-69.  doi:10.9767/bcrec.7.1.1631.59-69][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1631.59-69 ] | View in 

  19. Methanization, new opportunities for territories. National technical day - 13 May 2014, Paris. Collection of interventions. The Methanization Autonomy Nitrogen energy plan

    International Nuclear Information System (INIS)

    Bastide, Guillaume; Guilet, Marie; Banville, Sandrine; Rocher, Franck; Brosset, Denis; Chapelat, Nicolas; Le Roy, Philippe; Leboucher, Anne; Boucher, Sophie; Bolduan, Rainer; Pislor, Emilie; Desbles, Matthieu; Garoche, David; Decoopman, Bertrand; Deshayes, Odile; Mazzenga, Anthony; Quaak, Mauritz; Berthelot, Corinne

    2014-05-01

    This publication contains proceedings of a conference on methanization projects and techniques, notably in rural areas (there were 140 rural installations in France in 2014 and 20 centralised ones). Contributions thus give an overview of the present development of this sector, and of its perspectives over the medium to long term. A first set of contributions addressed the performance of a panel of farm-based and centralised methanization installations with technical, energy, environmental, agronomic and social assessments for 8 units (lessons learned from installation follow-up, recommendations for operation optimisation of 2 units), and a profitability study performed on 21 installations (lessons learned, profitability evolution for 2 installations). The second set of contributions addressed development perspectives of the methanization sector over the medium to long term. Contributions addressed the following issues: how to mobilise and process bio-wastes from big producers, other possible sources (energetic crops, intermediate crops for energy purposes or CIVE or crop residues), the use of digestate to reduce the use of mineral fertilizers, and emerging energetic valorisations of biogas. A last part presents the Methanization Autonomy Nitrogen Energy Plan (the EMAA plan) which aims at managing and valorising nitrogen (notably from breeding effluents), at developing a French model of agricultural methanization. The stakes of methanization for energy transition are outlined, and the operation of a methanization installation is described

  20. Syngas Production from CO2 Reforming and CO2-steam Reforming of Methane over Ni/Ce-SBA-15 Catalyst

    Science.gov (United States)

    Tan, J. S.; Danh, H. T.; Singh, S.; Truong, Q. D.; Setiabudi, H. D.; Vo, D.-V. N.

    2017-06-01

    This study compares the catalytic performance of mesoporous 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane reactions in syngas production. The catalytic performance of 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane was evaluated in a temperature-controlled tubular fixed-bed reactor at stoichiometric feed composition, 1023 K and atmospheric pressure for 12 h on-stream with gas hourly space velocity (GHSV) of 36 L gcat -1 h-1. The 10 Ni/Ce-SBA-15 catalyst possessed a high specific BET surface area and average pore volume of 595.04 m2 g-1. The XRD measurement revealed the presence of NiO phase with crystallite dimension of about 13.60 nm whilst H2-TPR result indicates that NiO phase was completely reduced to metallic Ni0 phase at temperature beyond 800 K and the reduction temperature relied on different degrees of metal-support interaction associated with the location and size of NiO particles. The catalytic reactivity was significantly enhanced with increasing H2O/CO2 feed ratio. Interestingly, the H2/CO ratio for CO2-steam reforming of methane varied between 1 and 3 indicated the occurrence of parallel reactions, i.e., CH4 steam reforming giving a H2/CO of 3 whilst reverse water-gas shift (RWGS) reaction consuming H2 to produce CO gaseous product.

  1. Eco-friendly synthesis and characterization of Ni-Si nanoparticles mixed oxides as catalyst for partial oxidation of methane

    International Nuclear Information System (INIS)

    Fakhroueian, Z.; Farzaneh, F.

    2009-01-01

    The nanoparticles of Ni-Si mixed oxides were prepared by co-precipitation method using nickel nitrate; Ni(NO 3 ) 2 6H 2 O and tetraethyl orthosilicate. The products were characterized by X-ray diffraction, transmission electron microscopy, and hydrogen temperature program reduction (H 2 -TPR). The results revealed that Ni-Si mixed oxides particles were obtained with average particle size 1-2 nm. The Ni-Si nanoparticles mixed oxides successfully catalyzed the partial oxidation of methane to hydrogen and carbon monoxide (Syn gas) using a fixed-bed reactor with about 92% activity and high selectivity. No coke formation and deactivation of catalyst were observed during the course of reaction. Particularly significant is the similar reactivity of this catalyst with that of Ni-Ce-Zr mixed oxides

  2. Ni-Pd-Al2O3 catalyst supported on reticulated ceramic foam for dry methane reforming

    Directory of Open Access Journals (Sweden)

    Vesna Nikolić

    2015-03-01

    Full Text Available In the present study, Ni-Pd/Al2O3 catalyst supported on α-Al2O3 based foam was prepared and evaluated in the dry methane reforming process. Corresponding metal chlorides were deposited to the foam surface by impregnation of the foam with ultrasonically aerosolized salt solutions at 473 K and drying at that temperature. Calcination step was excluded and the catalyst was reduced at very low temperature – 533 K. The reforming experiment lasted for 3 h, with standing time of 1 h at the following temperatures: 873, 973 and 1023 K. Conclusions on selectivity, catalytic activity and stability were reached on the basis of CO and H2 yields.

  3. Directly observing catalytic intermediates of methane dry reforming (MDR) on model Ni(111) catalyst via in operando surface techniques

    Science.gov (United States)

    Yuan, Kaidi

    In this work, near ambient pressure x-ray photoelectron spectroscopy was used to trace the in operando catalytic intermediates of methane dry reforming on model Ni(111) catalyst. The following reactive carbon intermediates have been characterized from dissociation of CH4: *CH, *C1 (Ni3C), *Cn (n≥2) and clock-reconstructed Ni2C. They can develop into inert graphene, and the conditions for this transition have been explored. One the other hand, the oxygen intermediates from CO2 dissociation were also studied, which play an important role on restraining graphene growth. Their dynamic coverage decreases with increasing temperature, which is suggested the fundamental mechanism of regional carbon overspill and causes irreversible graphene formation. Therefore, solutions based on Ni-O stabilization were proposed in developing coking resisting catalysts.

  4. Direct conversion of methane to higher hydrocarbons using AlBr3-HBr superacid catalyst.

    Science.gov (United States)

    Vasireddy, Sivakumar; Ganguly, Sreemoyee; Sauer, Joe; Cook, Wyndham; Spivey, James J

    2011-01-14

    The direct gas phase catalytic oligomerization of methane at temperatures ≤673 K has been demonstrated using AlBr(3)-HBr superacid. The reaction produces C(2)+ hydrocarbons and hydrogen in a single step at 1 atm in a continuous flow reactor at a nominal residence time of 60 s. The essentially complete conversion of methane appears to be due to protolytic activation of methane in the presence of H(+)AlBr(4)(-).

  5. Effect of zirconia morphology on sulfur-resistant methanation performance of MoO3/ZrO2 catalyst

    Science.gov (United States)

    Liu, Chen; Wang, Weihan; Xu, Yan; Li, Zhenhua; Wang, Baowei; Ma, Xinbin

    2018-05-01

    Two kinds of ZrO2 support with different morphologies were prepared by facile solvothermal method in different solvents. The obtained two supports showed monoclinic zirconia (m-ZrO2) and tetragonal zirconia (t-ZrO2) phase with similar crystalline size. Their supported Mo-based catalysts were prepared by impregnation method and the effect of zirconia morphology on the performance of sulfur-resistant methanation was examined. The results indicated that the MoO3/m-ZrO2 has higher CO conversion than the MoO3/t-ZrO2 catalyst. Characterizations by XRD, Raman, H2-TPR and IR confirmed that the m-ZrO2 is superior to t-ZrO2 for dispersing molybdenum species. In addition, the MoO3/m-ZrO2 catalyst has weaker interaction between support and active Mo speices than the MoO3/t-ZrO2 catalyst, which facilitates to forming active species of nanocrystalline MoS2 layers for sulfur-resistant methanation. The weaker interaction of molybdenum species with m-ZrO2 is related with the more covalent character of the Zrsbnd O bond and more oxygen defective structure of m-ZrO2. A larger number of Lewis acid centers appear on the surface of m-ZrO2, which verified the substantial vacancies on m-ZrO2 exposing coordinately unsaturated Zr3+ and Zr4+ cations. Meanwhile, the less Lewis acid of t-ZrO2 result in stronger interaction between support and molybdenum species and trigger crystalline phase MoO3 and Mosbnd Osbnd Zr linkages.

  6. A Study of CO2 Methanation over Ni-Based Catalysts Supported by CNTs with Various Textural Characteristics

    Directory of Open Access Journals (Sweden)

    Yanyan Feng

    2015-01-01

    Full Text Available This work studied the influence of textural characteristics of CNTs on catalytic performance of Ni/CNTs for CO2 methanation. The CNTs supports were prepared by chemical vapor deposition method using Ni/MgO catalysts, and acetonitrile and ethanol were used as carbon sources, respectively. The Ni/CNTs catalysts were prepared via impregnation method and characterized by X-ray diffraction (XRD, N2 adsorption/desorption, and temperature-programmed reduction (H2-TPR techniques. The results indicated that the textural characteristics of CNTs supports significantly impacted on the catalytic performance of Ni/CNTs. The catalyst Ni/CNTs-E (CNTs using ethanol as carbon source had good reducibility, high specific surface area, and moderate defects, resulting in higher CO2 conversion and CH4 yield, followed by Ni/CNTs-C (commercial CNTs and Ni/CNTs-A (CNTs using acetonitrile as carbon source. Based on Arrhenius formula, activation energies of the catalysts were calculated and were found decreased for Ni/CNTs-A and Ni/CNTs-E.

  7. Catalytic activity and effect of modifiers on Ni-based catalysts for the dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Barroso-Quiroga, Maria Martha; Castro-Luna, Adolfo Eduardo [Facultad de Ingenieria y Ciencias Economico-Sociales INTEQUI-CONICET-UNSL, Av. 25 de Mayo 384 (5730) Villa Mercedes (S.L.) (Argentina)

    2010-06-15

    Ni catalysts supported on different ceramic oxides (Al{sub 2}O{sub 3}, CeO{sub 2}, La{sub 2}O{sub 3}, ZrO{sub 2}) were prepared by wet impregnation. The catalytic behavior toward hydrogen production through the dry reforming of methane using a fixed-bed reactor was evaluated under certain experimental conditions, and the catalyst supported on ZrO{sub 2} showed the highest stable activity during the period of time studied. The catalyst supported on CeO{sub 2} has a relatively good activity, but shows signs of deactivation after a certain time during the reaction. This catalyst was chosen to be studied after the addition of 0.5 wt% Li and K as activity modifiers. The introduction of the alkaline metals produces a reduction of the catalytic activity but a better stability over the reactant conversion time. The reverse water-gas shift reaction influences the global system of reactions, and as the results indicate, should be considered near equilibrium. (author)

  8. Highly stable ceria-zirconia-yttria supported Ni catalysts for syngas production by CO2 reforming of methane

    Science.gov (United States)

    Muñoz, M. A.; Calvino, J. J.; Rodríguez-Izquierdo, J. M.; Blanco, G.; Arias, D. C.; Pérez-Omil, J. A.; Hernández-Garrido, J. C.; González-Leal, J. M.; Cauqui, M. A.; Yeste, M. P.

    2017-12-01

    Ni/CeO2/YSZ and Ni/Ce0.15Zr0.85O2 have been investigated as catalysts for the dry reforming of methane at 750 °C. Ni was incorporated by the impregnation method. The supports were previously activated by using a thermo-chemical protocol consisting on a severe reduction (H2/Ar) at 950 °C followed by a mild oxidation (O2/He) at 500 °C. According to TPR results, this protocol leads to the development of unique redox properties in the case of the CeO2/YSZ oxide. Two types of CO2 + CH4 (1:1) mixtures (helium-diluted and undiluted) were used to feed the reactor. When using the Ni/Ce0.15Zr0.85O2 catalyst with undiluted feed, the reactor became plugged by coke. By contrast, Ni/CeO2/YSZ behaved as an active and stable catalyst even under the most severe operation conditions. The characterization of the spent Ni/CeO2/YSZ using TGA, TEM, Raman and XPS spectroscopy revealed that only a limited amount of graphitic carbon, in form of nanotubes, was formed. No evidences of deactivating carbonaceous forms were obtained. The singular redox properties of the activated CeO2/YSZ oxides are proposed as a key for designing Ni catalysts highly stable in reforming processes.

  9. Critical Surface Parameters for the Oxidative Coupling of Methane over the Mn-Na-W/SiO2 Catalyst.

    Science.gov (United States)

    Hayek, Naseem S; Lucas, Nishita S; Warwar Damouny, Christine; Gazit, Oz M

    2017-11-22

    The work here presents a thorough evaluation of the effect of Mn-Na-W/SiO 2 catalyst surface parameters on its performance in the oxidative coupling of methane (OCM). To do so, we used microporous dealuminated β-zeolite (Zeo), or mesoporous SBA-15 (SBA), or macroporous fumed silica (Fum) as precursors for catalyst preparation, together with Mn nitrate, Mn acetate and Na 2 WO 4 . Characterizing the catalysts by inductively coupled plasma-optical emission spectroscopy, N 2 physisorption, X-ray diffraction, high-resolution scanning electron microscopy-energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and catalytic testing enabled us to identify critical surface parameters that govern the activity and C 2 selectivity of the Mn-Na-W/SiO 2 catalyst. Although the current paradigm views the phase transition of silica to α-cristobalite as the critical step in obtaining dispersed and stable metal sites, we show that the choice of precursors is equally or even more important with respect to tailoring the right surface properties. Specifically, the SBA-based catalyst, characterized by relatively closed surface porosity, demonstrated low activity and low C 2 selectivity. By contrast, for the same composition, the Zeo-based catalyst showed an open surface pore structure, which translated up to fourfold higher activity and enhanced selectivity. By varying the overall composition of the Zeo catalysts, we show that reducing the overall W concentration reduces the size of the Na 2 WO 4 species and increases the catalytic activity linearly as much as fivefold higher than the SBA catalyst. This linear dependence correlates well to the number of interfaces between the Na 2 WO 4 and Mn 2 O 3 species. Our results combined with prior studies lead us to single out the interface between Na 2 WO 4 and Mn 2 O 3 as the most probable active site for OCM using this catalyst. Synergistic interactions between the various precursors used and the phase transition are discussed in

  10. Partial oxidation of methane to syngas on Rh/Al{sub 2}O{sub 3} and Rh/Ce-ZrO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Raquel L.; Bitencourt, Isabela G.; Passos, Fabio B., E-mail: fbpassos@vm.uff.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e Petroleo

    2013-01-15

    The partial oxidation of methane with {gamma}-Al{sub 2}O{sub 3}-, CeO{sub 2}-, ZrO{sub 2}- and Ce-ZrO{sub 2}-supported rhodium catalysts was investigated. DRIFTS (diffuse reflectance infrared spectroscopy) measurements of adsorbed CO showed the formation of different rhodium species on different supports, which influenced the dispersion of the metal. The effects of the metal dispersion, oxygen storage capacity on the activity of these catalysts for the partial oxidation of methane are discussed. (author)

  11. Effect of nitrogen-containing impurities on the activity of perovskitic catalysts for the catalytic combustion of methane.

    Science.gov (United States)

    Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia

    2012-11-05

    LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.

  12. A comparative parametric study of a catalytic plate methane reformer coated with segmented and continuous layers of combustion catalyst for hydrogen production

    Science.gov (United States)

    Mundhwa, Mayur; Parmar, Rajesh D.; Thurgood, Christopher P.

    2017-03-01

    A parametric comparison study is carried out between segmented and conventional continuous layer configurations of the coated combustion-catalyst to investigate their influence on the performance of methane steam reforming (MSR) for hydrogen production in a catalytic plate reactor (CPR). MSR is simulated on one side of a thin plate over a continuous layer of nickel-alumina catalyst by implementing an experimentally validated surface microkinetic model. Required thermal energy for the MSR reaction is supplied by simulating catalytic methane combustion (CMC) on the opposite side of the plate over segmented and continuous layer of a platinum-alumina catalyst by implementing power law rate model. The simulation results of both coating configurations of the combustion-catalyst are compared using the following parameters: (1) co-flow and counter-flow modes between CMC and MSR, (2) gas hourly space velocity and (3) reforming-catalyst thickness. The study explains why CPR designed with the segmented combustion-catalyst and co-flow mode shows superior performance not only in terms of high hydrogen production but also in terms of minimizing the maximum reactor plate temperature and thermal hot-spots. The study shows that the segmented coating requires 7% to 8% less combustion-side feed flow and 70% less combustion-catalyst to produce the required flow of hydrogen (29.80 mol/h) on the reforming-side to feed a 1 kW fuel-cell compared to the conventional continuous coating of the combustion-catalyst.

  13. Catalytic combustion of lean methane at low temperature over ZrO2-modified Co3O4 catalysts

    Science.gov (United States)

    Pu, Zhiying; Liu, Yan; Zhou, Huan; Huang, Wanzhen; Zheng, Yifan; Li, Xiaonian

    2017-11-01

    A series of ZrO2 modified Co3O4 catalysts prepared by co-precipitation method were characterized by XRD, Raman, SEM, XPS and H2-TPR, and used in the catalytic combustion of lean methane at low temperature. XRD and Raman results demonstrate that ZrO2sbnd Co3O4 is in the form of a Zr-Co-O solid solution. XPS result indicates that the content of ZrO2 in ZrO2sbnd Co3O4 composite oxide has a significant influence on the concentration of Co2+ in tetrahedral site (ATetrahedral/AOctahedral) and the surface active oxygen species, which are correlated to the activity of methane combustion. H2-TPR result shows that the ZrO2(2)-Co3O4 composite oxide exhibits better reducibility. Compared with pure Co3O4, the ZrO2(2)-Co3O4 composite oxide presented the highest activity with T90 of 335 °C. All these characterizations suggest that high activity in the lean methane combustion could be ascribed to high surface areas, ATetrahedral/AOctahedral and surface active oxygen species.

  14. Catalyst evaluation for high-purity H2 production by sorption-enhanced steam-methane reforming coupled to a Ca/Cu process

    Science.gov (United States)

    Navarro, M. V.; López, J. M.; García, T.; Grasa, G.; Murillo, R.

    2017-09-01

    The operational limits of a commercial nickel-based catalyst under the conditions of a sorption-enhanced steam-methane reforming process coupled to a Ca/Cu chemical loop are investigated for high-purity H2 production in a cyclic operation. The performance of the reforming catalyst is tested by means of a high number of oxidation-reduction-reforming cycles. After 100 oxidation-reduction cycles, this catalyst retains its exceptional reforming activity. The methane conversion values are close to the thermodynamic equilibrium under very demanding conditions: temperature between 500 °C - 700 °C and mass hourly space velocity of 8.8 kgCH4 h-1 kgcat-1. After 200 cycles, the sample shows reduction in its reforming activity in line with a lower dispersion of the Ni species. Sintering of Ni nanocrystals is evidenced during the oxidation-reduction multi-cycles. The performance of the catalyst after 200 oxidation-reduction cycles mixed with a CaO-based CO2 sorbent is studied under optimal conditions calculated for the sorption-enhanced reforming process coupled to a Ca/Cu cycle (temperature of 650 °C, steam/methane ratio of 4, sorbent/catalyst ratio of 4 and space velocity of 0.75 kgCH4 h-1 kgcat-1). Remarkably, an equilibrium value over 92 vol.% H2 concentration is achieved, highlighting this catalyst as a promising candidate for the next steps of the process development.

  15. Influence of the catalyst type on the growth of carbon nanotubes via methane chemical vapor deposition

    NARCIS (Netherlands)

    Jodin, Lucie; Dupuis, Anne-Claire; Rouvière, Emmanuelle; Reiss, Peter

    2006-01-01

    The preparation of the catalyst is one of the key parameters which governs the quality of carbon nanotubes (CNTs) grown by catalyzed chemical vapor deposition (CVD). We investigated the influence of three different procedures of catalyst preparation on the type and diameter of CNTs formed under

  16. Highly sensitive methane catalytic combustion micro-sensor based on mesoporous structure and nano-catalyst.

    Science.gov (United States)

    Su, Jiacan; Cao, Liehu; Li, Liang; Wei, Jie; Li, Gengnan; Yuan, Yinyin

    2013-10-21

    In order to get a methane catalytic combustion micro-sensor, two different catalytic systems used in traditional methane catalytic combustion sensors were fabricated into a mesoporous structure and their catalytic activities were investigated. In comparison, the Rh2O3-Al2O3 system can form more a uniform mesoporous structure and has a much higher specific surface area. Even more importantly, it has relatively higher catalytic activity and stability for the methane catalytic combustion reaction. After being coated on a microelectro-mechanical system (MEMS) micro-heater, a catalytic combustion type methane micro-sensor was fabricated. The meso-structured Rh2O3-Al2O3 hybrid based MEMS sensor demonstrated a short T90 response time, relatively high signal output, high enough signal/noise ratio for practical detecting and strong anti-poison properties.

  17. Ni-SiO2 Catalysts for the Carbon Dioxide Reforming of Methane: Varying Support Properties by Flame Spray Pyrolysis

    Directory of Open Access Journals (Sweden)

    Emma C. Lovell

    2015-03-01

    Full Text Available Silica particles were prepared by flame spray pyrolysis (FSP as a support for nickel catalysts. The impact of precursor feed rate (3, 5 and 7 mL/min during FSP on the silica characteristics and the ensuing effect on catalytic performance for the carbon dioxide, or dry, reforming of methane (DRM was probed. Increasing the precursor feed rate: (i progressively lowered the silica surface area from ≈340 m2/g to ≈240 m2/g; (ii altered the silanol groups on the silica surface; and (iii introduced residual carbon-based surface species to the sample at the highest feed rate. The variations in silica properties altered the (5 wt % nickel deposit characteristics which in turn impacted on the DRM reaction. As the silica surface area increased, the nickel dispersion increased which improved catalyst performance. The residual carbon-based species also appeared to improve nickel dispersion, and in turn catalyst activity, although not to the same extent as the change in silica surface area. The findings illustrate both the importance of silica support characteristics on the catalytic performance of nickel for the DRM reaction and the capacity for using FSP to control these characteristics.

  18. The effect of Sc promoter on the performance of Co/TiO{sub 2}–P25 catalyst in dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Al-fatesh, Ahmed Sadeq; Naeem, Muhammad Awais; Fakeeha, Anis Hamza; Abasaeed, Ahmed Elhag [Dept. of Chemical Engineering, College of Engineering, King Saud University, Riyadh (Saudi Arabia)

    2015-08-15

    In the present work, the effect of scandium (Sc) promoter on the performance of Co/TiO{sub 2}–P25 catalyst in dry reforming of methane has been investigated. The catalysts were prepared by the incipient wet impregnation technique. For each catalyst, the Co loading was fixed at 5 wt %, while the Sc loading was varied from 0.0 to 2.0 wt %. The experiments were carried out at atmospheric pressure in a micro tubular reactor at a temperature of 700 °C. For better understanding and comparison, the catalysts were characterized by various techniques such as Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), H{sub 2}-temperature-programmed reduction (TPR), CO{sub 2}-temperature-programmed desorption (TPD), and thermogravimetric analyses (TGA). The results revealed that the promotion of Co/TiO{sub 2}–P25 catalyst with Sc has a significant impact on its catalytic performance and the amount of carbon deposition. The doping of Co/TiO{sub 2}–P25 catalyst with Sc improves the basicity and enhances the metal support interaction in the catalyst. At higher Sc loading, Co metal oxidation became substantial that triggered severe catalyst deactivation. Amongst all Sc-promoted catalysts, 0.75 wt % Sc-promoted catalyst exhibited the highest CH{sub 4} and CO{sub 2} activity with minimum deactivation.

  19. Effects of FeO{sub x}, CoO{sub x}, and NiO catalysts and calcination temperatures on the synthesis of single-walled carbon nanotubes through chemical vapor deposition of methane

    Energy Technology Data Exchange (ETDEWEB)

    Tan, S.-M. [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S. Pulau Pinang (Malaysia); Chai, S.-P. [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S. Pulau Pinang (Malaysia); School of Engineering, Monash University, Jalan Lagoon Selatan, 46150 Bandar Sunway, Selangor (Malaysia); Liu, W.-W. [School of Materials Science and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S. Pulau Pinang (Malaysia); Mohamed, Abdul Rahman [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S. Pulau Pinang (Malaysia)], E-mail: chrahman@eng.usm.my

    2009-05-27

    The oxides of cobalt, iron, and nickel catalysts were tested in chemical vapor deposition (CVD) of methane in synthesizing single-walled carbon nanotubes (SWNTs). All catalysts used in this study were prepared using impregnation method and calcined at temperatures ranging from 300 to 850 deg. C. The catalyst samples after CVD of methane were characterized using transmission electron microscopy (TEM). The TEM study elucidates that iron oxide serves as an effective catalyst for growing SWNTs. The presence of SWNTs on the catalyst was confirmed in the Raman study.

  20. Effects of FeOx, CoOx, and NiO catalysts and calcination temperatures on the synthesis of single-walled carbon nanotubes through chemical vapor deposition of methane

    International Nuclear Information System (INIS)

    Tan, S.-M.; Chai, S.-P.; Liu, W.-W.; Mohamed, Abdul Rahman

    2009-01-01

    The oxides of cobalt, iron, and nickel catalysts were tested in chemical vapor deposition (CVD) of methane in synthesizing single-walled carbon nanotubes (SWNTs). All catalysts used in this study were prepared using impregnation method and calcined at temperatures ranging from 300 to 850 deg. C. The catalyst samples after CVD of methane were characterized using transmission electron microscopy (TEM). The TEM study elucidates that iron oxide serves as an effective catalyst for growing SWNTs. The presence of SWNTs on the catalyst was confirmed in the Raman study.

  1. Reaction path of the oxidative coupling of methane over a lithium-doped magnesium oxide catalyst : Factors affecting the Rate of Total Oxidation of Ethane and Ethylene

    NARCIS (Netherlands)

    Roos, J.A.; Korf, S.J.; Veehof, R.H.J.; van Ommen, J.G.; Ross, J.R.H.

    1989-01-01

    Experiments using gas mixtures of O2, C2H6 or C2H4 and CH4 or He have been carried out with a Li/MgO catalyst using a well-mixed reaction system which show that the total oxidation products, CO and CO2, are formed predominantly from ethylene, formed in the oxidative coupling of methane. It is

  2. A Green Process for High-Concentration Ethylene and Hydrogen Production from Methane in a Plasma-Followed-by-Catalyst Reactor

    International Nuclear Information System (INIS)

    Wang Kangjun; Li Xiaosong; Zhu Aimin

    2011-01-01

    A green process for the oxygen-free conversion of methane to high-concentration ethylene and hydrogen in a plasma-followed-by-catalyst (PFC) reactor is presented. Without any catalysts and with pure methane used as the feed gas, a stable kilohertz spark discharge leads to an acetylene yield of 64.1%, ethylene yield of 2.5% and hydrogen yield of 59.0% with 80.0% of methane conversion at a methane flow rate of 50 cm 3 /min and a specific input energy of 38.4 kJ/L. In the effluent gas from a stable kilohertz spark discharge reactor, the concentrations of acetylene, ethylene and hydrogen were 18.1%, 0.7% and 66.9%, respectively. When catalysts Pd-Ag/SiO 2 were employed in the second stage with discharge conditions same as in the case of plasma alone, the PFC reactor provides an ethylene yield of 52.1% and hydrogen yield of 43.4%. The concentrations of ethylene and hydrogen in the effluent gas from the PFC reactor were found to be as high as 17.1% and 62.6%, respectively. Moreover, no acetylene was detected in the effluent gas. This means that a high concentration of ethylene and oxygen-free hydrogen can be co-produced directly from methane in the PFC reactor.

  3. Unsupported NiPt alloy metal catalysts prepared by water-in-oil (W/O) microemulsion method for methane cracking

    KAUST Repository

    Zhou, Lu

    2016-05-18

    Unsupported NiPt metal catalyst with Ni/Pt molar ratio of 88/12 is prepared by water-in-oil (W/O) microemulsion method in this study. Compared to monometallic Ni and Pt catalysts, the NiPt catalyst exhibits superior activity and stability for methane cracking. By XRD (X-ray powder diffraction), XPS (X-ray photoelectron spectroscopy) and TEM (Transmission electron microscopy) analyses, the formation of Ni(0)Pt(0) alloy is believed to be the main reason for the reactivity improvement of this catalyst. Carbon nano tube (CNT) with Ni(0)Pt(0) particles anchored on the top of tube are found for the NiPt catalyst. © 2016 Elsevier Ltd.

  4. Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

    Science.gov (United States)

    Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

    2017-08-30

    Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.

  5. Effect of redox additives over Ni/Al{sub 2}O{sub 3} catalysts on syngas production via methane catalytic partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    J. Requies; V.L. Barrio; J.F. Cambra; M.B. Guemez; P.L. Arias; V. La Parola; M.A. Pena; J.L.G. Fierro [University of the Basque Country, Bilbao (Spain). School of Engineering

    2008-11-15

    Alumina-supported nickel catalysts modified with redox (Mo, Mn and Sn) oxides were tested in the catalytic partial oxidation (CPO) of methane and the wet catalytic partial oxidation (wet-CPO) of methane for syngas production. The influence of different reaction parameters on the performance of these systems was studied for both reactions. Certain insights on catalyst surface structure were revealed by means of X-ray photoelectron spectroscopy (XPS) and thermal programmed reduction (TPR). The joint analysis of all the results led to certain correlations between the structure of the catalysts and catalytic activity, indicating that the redox additives to some extent modify the stability of the active nickel phase by altering the nickel-alumina interface interaction. 37 refs., 9 figs., 4 tabs.

  6. Physico-chemical characterisations and catalytic performance of Ni-based catalyst systems for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Vlach, K.; Hoang, D.L.; Schneider, M.; Pohl, M.M.; Armbruster, U.; Martin, A. [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse e.V.

    2012-07-01

    In this study, ternary perovskite type oxides LaNi{sub x}Cu{sub 1-x}O{sub 3} (x = 0, 0.2, 0.5, 0.8, 1) were synthesized using NaOH and diethylenetriaminepentaacetic acid (H{sub 5}DTPA). The catalysts resulting from perovskite precursors exhibit catalytic activities for CO{sub 2} reforming of CH{sub 4} at 700 C that increase with a higher Ni content. Characterization methods showed that the activation led to formation of small metallic Ni/Cu particles. Methane and carbon dioxide conversions varied from 20 to 65% for CH{sub 4} and 3 to 58% for CO{sub 2}. Selectivities from 46 to 93% for CO and from 4 to 64% for H{sub 2} were obtained. (orig.)

  7. Methane-rich syngas production from hydrocarbon fuels using multi-functional catalyst/capture agent

    Energy Technology Data Exchange (ETDEWEB)

    Siefert, Nicholas S.; Shekhawat, Dushyant; Berry, David A.; Surdoval, Wayne A.

    2017-02-07

    The disclosure provides a gasification process for the production of a methane-rich syngas at temperatures exceeding 400.degree. C. through the use of an alkali hydroxide MOH, using a gasification mixture comprised of at least 0.25 moles and less than 2 moles of water for each mole of carbon, and at least 0.15 moles and less than 2 moles of alkali hydroxide MOH for each mole of carbon. These relative amounts allow the production of a methane-rich syngas at temperatures exceeding 400.degree. C. by enabling a series of reactions which generate H.sub.2 and CH.sub.4, and mitigate the reforming of methane. The process provides a methane-rich syngas comprised of roughly 20% (dry molar percentage) CH.sub.4 at temperatures above 400.degree. C., and may effectively operate within an IGFC cycle at reactor temperatures between 400-900.degree. C. and pressures in excess of 10 atmospheres.

  8. Development of Ni-Based Catalysts Derived from Hydrotalcite-Like Compounds Precursors for Synthesis Gas Production via Methane or Ethanol Reforming

    Directory of Open Access Journals (Sweden)

    Ya-Li Du

    2017-02-01

    Full Text Available As a favorably clean fuel, syngas (synthesis gas production has been the focus of concern in past decades. Substantial literatures reported the syngas production by various catalytic reforming reactions particularly in methane or ethanol reforming. Among the developed catalysts in these reforming processes, Ni-based catalysts from hydrotalcite-like compounds (HTLcs precursors have drawn considerable attention for their preferable structural traits. This review covers the recent literature reporting syngas production with Ni-based catalysts from HTLc precursors via methane or ethanol reforming. The discussion was initiated with catalyst preparation (including conventional and novel means, followed by subsequent thermal treatment processes, then composition design and the addition of promoters in these catalysts. As Ni-based catalysts have thermodynamic potential to deactivate because of carbon deposition or metal sintering, measures for dealing with these problems were finally summarized. To obtain optimal catalytic performances and resultantly better syngas production, based on analyzing the achievements of the references, some perspectives were finally proposed.

  9. Facile and large-scale synthesis of high quality few-layered graphene nano-platelets via methane decomposition over unsupported iron family catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Awadallah, Ahmed E., E-mail: ahmedelsayed_epri@yahoo.com [Process Development Division, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Aboul-Enein, Ateyya A. [Process Development Division, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Kandil, Usama F. [Petroleum Application Department, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Taha, Mahmoud Reda [Department of Civil Engineering, University of New Mexico, Albuquerque, NM 87131 (United States)

    2017-04-15

    High quality few-layered graphene nano-platelets (GNPs) were successfully prepared via catalytic chemical vapor deposition of methane under ambient pressure using substrate-free unsupported iron, cobalt, and nickel metallic sheets as catalysts. The bulk catalysts were prepared via combustion method using citric acid as a fuel. Various analytical techniques, including high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), temperature programmed reduction (TPR) and Raman spectroscopy were employed to characterize the fresh and reduced catalysts and to identify the morphological structure of the as-grown GNPs. TEM images of the reduced metal catalysts showed that polycrystalline metallic sheets were easily produced after complete reduction of unsupported metal oxides. The data demonstrated that the formation of zero-valent metallic sheets could effectively promote the growth of GNPs on their surfaces. The unsupported Ni catalyst exhibits higher catalytic growth activity in terms of GNPs yield (254 wt%) compared with all other catalysts. Raman spectra and TEM results established that a few layers of GNPs with high crystallinity and good graphitization were produced. TGA results further demonstrated that the as-grown GNPs exhibit significantly higher thermal stability in air atmosphere compared with other synthesis methods. - Highlights: • Few-layered graphene nanoplatelets were prepared via methane catalytic decomposition. • Metallic sheets of iron group metals were used as novel catalysts. • The surfaces of metallic sheets were found to be very effective for GNPs growth. • The number of layers is dependent on the morphological structure of the catalysts. • The unsupported metallic Ni catalyst exhibited higher catalytic growth activity.

  10. Facile and large-scale synthesis of high quality few-layered graphene nano-platelets via methane decomposition over unsupported iron family catalysts

    International Nuclear Information System (INIS)

    Awadallah, Ahmed E.; Aboul-Enein, Ateyya A.; Kandil, Usama F.; Taha, Mahmoud Reda

    2017-01-01

    High quality few-layered graphene nano-platelets (GNPs) were successfully prepared via catalytic chemical vapor deposition of methane under ambient pressure using substrate-free unsupported iron, cobalt, and nickel metallic sheets as catalysts. The bulk catalysts were prepared via combustion method using citric acid as a fuel. Various analytical techniques, including high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), temperature programmed reduction (TPR) and Raman spectroscopy were employed to characterize the fresh and reduced catalysts and to identify the morphological structure of the as-grown GNPs. TEM images of the reduced metal catalysts showed that polycrystalline metallic sheets were easily produced after complete reduction of unsupported metal oxides. The data demonstrated that the formation of zero-valent metallic sheets could effectively promote the growth of GNPs on their surfaces. The unsupported Ni catalyst exhibits higher catalytic growth activity in terms of GNPs yield (254 wt%) compared with all other catalysts. Raman spectra and TEM results established that a few layers of GNPs with high crystallinity and good graphitization were produced. TGA results further demonstrated that the as-grown GNPs exhibit significantly higher thermal stability in air atmosphere compared with other synthesis methods. - Highlights: • Few-layered graphene nanoplatelets were prepared via methane catalytic decomposition. • Metallic sheets of iron group metals were used as novel catalysts. • The surfaces of metallic sheets were found to be very effective for GNPs growth. • The number of layers is dependent on the morphological structure of the catalysts. • The unsupported metallic Ni catalyst exhibited higher catalytic growth activity.

  11. Electrochemical promotion of oxidative coupling of methane on platinum/polybenzimidazole catalyst

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Bjerrum, Niels

    2002-01-01

    , meaning that there was a maximum promotion effect at a polarization of -0.15 V, or 0.45 V catalyst potential vs. a hydrogen electrode (3.8% C2H2 yield). The catalytic rate enhancement ratio, r(C-2)/r(o)(C-2), at this maximum was 4.2. There was no C2H2 production at polarization greater than or equal to0......), at this maximum was 1.1, which means that this catalytic reaction is only slightly affected by the electrochemical polarization. This indicates that polarization especially affects the C-2 selectivity of the catalyst. The obtained data was explained by the electrochemical production of Pt-H active centers...... at the electrolyte-catalyst-gaseous reactant interface (lambda much greater than 1)....

  12. Making fired bricks with spent equilibrium catalyst-a technical feasibility study

    Science.gov (United States)

    Chou, M.-L.; Chen, L.-M.; Lai, Y.-C.; Chou, S.-F.

    2009-01-01

    Fluid catalytic cracking in an oil refinery uses a catalyst, such as an alumino-silicate zeolite, in the conversion of heavy hydrocarbons to light hydrocarbons. A small fraction of the catalyst is continually replaced with fresh catalyst to maintain activity. In North America, more than 400 tons of spent alumino-silicate equilibrium catalyst (spent e-cat), and worldwide, more than 1,100 tons, are generated daily, most of which is disposed of in landfills (municipal and on-site facilities). In this study, three spent e-cat samples were tested in a value-added application that would utilize this waste in the manufacturing of fired bricks. The results of this study indicate that spent e-cat is a technically feasible raw material substitute for the clay and shale commonly used in fired brick production. Fired bricks produced with up to 30 wt% of spent e-cat showed good physical appearance and their water absorption properties met the ASTM C 62 specifications for building bricks of either the moderate-or severe-weathering grade.

  13. Kinetics of methane decomposition to CO{sub x}-free hydrogen and carbon nanofiber over Ni-Cu/MgO catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Borghei, Maryam; Karimzadeh, Ramin [Chemical Engineering Department, Tarbiat Modares University, Tehran (Iran); Rashidi, Alimorad; Izadi, Nosrat [Research Center of Nanotechnology, Research Institute of Petroleum Industry, Tehran (Iran)

    2010-09-15

    Kinetic modeling of methane decomposition to CO{sub x}-free hydrogen and carbon nanofiber has been carried out in the temperature range 550-650 C over Ni-Cu/MgO catalyst from CH{sub 4}-H{sub 2} mixtures at atmospheric pressure. Assuming the different mechanisms of the reaction, several kinetic models were derived based on Langmuir-Hinshelwood type. The optimum value of kinetic parameters has been obtained by Genetic Algorithm and statistical analysis has been used for the model discrimination. The suggested kinetic model relates to the mechanism when the dissociative adsorption of methane molecule is the rate-determining stage and the estimated activation energy is 50.4 kJ/mol in agreement with the literature. The catalyst deactivation was found to be dependent on the time, reaction temperature, and partial pressures of methane and hydrogen. Inspection of the behavior of the catalyst activity in relation to time, led to a model of second order for catalyst deactivation. (author)

  14. Toward computational screening in heterogeneous catalysis: Pareto-optimal methanation catalysts

    DEFF Research Database (Denmark)

    Andersson, Martin; Bligaard, Thomas; Kustov, Arkadii

    2006-01-01

    Finding the solids that are the best catalysts for a given reaction is a daunting task due to the large number of combinations and structures of multicomponent Surfaces. In addition, it is not only the reaction rate that needs to be optimized: the selectivity. durability. and cost Must also be ta...

  15. Comparison Of Different Noble Metal Catalysts For The Low Temperature Catalytic Partial Oxidation Of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Rabe, S.; Truong, T.-B.; Vogel, F.

    2005-03-01

    The generation of synthesis gas at low temperatures can contribute to a more economic production of clean transportation fuels (Fischer-Tropsch liquids) from natural gas. In this report, the performance of different noble metal catalysts in a low temperature catalytic partial oxidation process is presented. (author)

  16. Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts

    DEFF Research Database (Denmark)

    Peterson, Andrew; Nørskov, Jens K.

    2012-01-01

    The electrochemical reduction of CO2 into hydrocarbons and alcohols would allow renewable energy sources to be converted into fuels and chemicals. However, no electrode catalysts have been developed that can perform this transformation with a low overpotential at reasonable current densities. In ...

  17. Visualizing a Catalyst at Work during the Ignition of the Catalytic Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Kimmerle, Bertram; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2009-01-01

    We present a spatiotemporal operando X-ray absorption study of a highly dynamic process, the ignition of the noble metal catalyzed partial oxidation of methane. Evolvement and propagation of the platinum component's structural changes are investigated with a high-speed X-ray camera, which in comb...... in combination with temperature profiling by IR-thermography and catalytic activity measurements by online mass spectrometry gives insight into the first stages of the ignition of the reaction toward hydrogen and carbon monoxide....

  18. An anodic alumina supported Ni-Pt bimetallic plate-type catalysts for multi-reforming of methane, kerosene and ethanol

    KAUST Repository

    Zhou, Lu

    2014-05-01

    An anodic alumina supported Ni-Pt bimetallic plate-type catalyst was prepared by a two-step impregnation method. The trace amount 0.08 wt% of Pt doping efficiently suppressed the nickel particle sintering and improved the nickel oxides reducibility. The prepared Ni-Pt catalyst showed excellent performance during steam reforming of methane, kerosene and ethanol under both 3000 h stationary and 500-time daily start-up and shut-down operation modes. Self-activation ability of this catalyst was evidenced, which was considered to be resulted from the hydrogen spillover effect over Ni-Pt alloy. In addition, an integrated combustion-reforming reactor was proposed in this study. However, the sintering of the alumina support is still a critical issue for the industrialization of Ni-Pt catalyst. Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  19. Research of Coalbed Methane Development Well-Type Optimization Method Based on Unit Technical Cost

    Directory of Open Access Journals (Sweden)

    Shiqun Li

    2016-08-01

    Full Text Available Coalbed Methane (CBM is a high-quality unconventional energy resource. The successful development and utilization of a CBM resource needs to consider technical feasibility and economic viability. These factors are also necessary for the improvement of production safety in coal mines, reducing carbon emission, and optimizing energy structure. Because of its unique resource characteristics, surface drilling is the prevailing development approach all over the world. Directional and horizontal wells are generally the two major well-types for CBM development. Development well-type is an important factor affecting CBM efficient development, as it is a key factor in the process of the economic and effective development of CBM resource. In this paper, a method based on Unit Technical Cost (UTC will be constructed from the perspective of economic viability, and will be used for more simple and accurate optimization of CBM. This method is used for practical well-type optimization in two major CBM development basins in China, and the application results prove that this method is scientifically accurate and feasible.

  20. Ultrasound assisted dispersion of different amount of Ni over ZSM-5 used as nanostructured catalyst for hydrogen production via CO2 reforming of methane

    International Nuclear Information System (INIS)

    Vafaeian, Yaser; Haghighi, Mohammad; Aghamohammadi, Sogand

    2013-01-01

    Graphical abstract: A series of Ni/ZSM-5 nanocatalysts with different amount of Ni were prepared via ultrasound assisted method and characterized with XRD, FESEM, TEM, BET and FTIR techniques. The research deals with catalyst development for dry reforming of methane with the aim of reaching the most stable catalyst specifically over nano-sized catalysts. About more than 99% of Ni particles size is less than 100 nm for the sample prepared with 8% Ni, which is essential to the relative suppression of the carbon formation on catalysts. Catalyst prepared with 8% Ni content showed superior activity in process expected due to its better catalytic properties. - Highlights: • Using ZSM-5 zeolite in dry reforming of methane. • Employing ultrasound energy in synthesis of Ni/ZSM-5 nanocatalyst. • Enhancement of Ni particles size to meet desired catalyst at lower amount of Ni loading. • Dry reforming of methane over Ni/ZSM-5 nanocatalyst with different Ni-loading. • Superior activity of Ni/ZSM-5 nanocatalyst synthesized with 8% Ni content. - Abstract: Carbon dioxide reforming of methane is an interesting route for synthesis gas production especially over nanostructured catalysts. The present research deals with nanocatalyst development by sonochemical method for dry reforming of methane with the aim of reaching the most efficient nanocatalyst. Effect of Ni metal content, one of the most significant variables, on the properties of the ZSM-5 supported nanocatalysts was taken into account. The Ni/ZSM-5 nanocatalysts were prepared via assisted traditional impregnation method via ultrasound irradiation and characterized with XRD, FESEM, TEM, BET and FTIR techniques. Comparison of XRD patterns implies that the peaks related to NiO become sharper by increasing metal content over the support. In the case of nanocatalysts with lower metal content (3% and 8%), the beneficial influence of ultrasound assisted procedure become more pronounced and the observed reduction in

  1. Technology development for cobalt F-T catalysts. Quarterly technical progress report No. 12, July 1, 1995--September 30, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Singleton, A.H.

    1996-03-21

    The investigation of the effect of certain promoters (Fe, Pd, and Ru) on the deactivation characteristics of Co catalysts during F-T synthesis was continued during this reporting period. All catalysts were tested first at 220{degrees}C, then at higher temperatures from 240 to 280{degrees}C, while monitoring their deactivation. The choice of these promoters was based on their intrinsic ability to enhance the hydrogenation reactions while slowing down the Boudouard reaction under the conditions used in F-T synthesis. Olefin hydrogenation and CO dissociation reactions were used individually to investigate further the nature of the deactivation process of these catalyst during F-T synthesis. Hydrogenation of isobutene (IB) was carried out in the presence of CO between 120 and 180{degrees}C and atmospheric pressure. CO dissociation activities of the catalysts were measured using a pulse technique at 2.5 atm and at temperatures between 180 and 280{degrees}C with intermittent H{sub 2} bracketing at 350{degrees}C. Promotion with high loadings of Fe or Pd resulted in catalysts with relatively lower activity and higher methane selectivity. The deactivation process and rate for catalysts containing Pd or Fe were similar to those of the non-promoted or Ru-promoted alumina-supported Co catalysts tested previously. The only exception was Co.068 with 1% Pd which had adequate activity and selectivity as well as lower deactivation rate at the various temperatures tested.

  2. Dry (CO{sub 2}) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Juntian [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Du, Xuesen, E-mail: xuesendu@cqu.edu.cn [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Ran, Jingyu, E-mail: jyran@189.cn [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China); Wang, Ruirui [Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Ministry of Education of PRC, Chongqing University, Chongqing, 400044 (China); College of Power Engineering, Chongqing University, Chongqing, 400044 (China)

    2016-07-15

    Graphical abstract: - Highlights: • CH appears to be the most abundant species on Pt(1 1 1) surface in CH{sub 4} dissociation. • CO{sub 2}* + H* → COOH* + * → CO* + OH* is the dominant reaction pathway in CO{sub 2} activation. • Major reaction pathway in CH oxidation: CH* + OH* → CHOH* + * → CHO* + H* → CO* + 2H*. • C* + OH* → COH* + * → CO* + H* is the dominant reaction pathway in C oxidation. - Abstract: Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H{sub 2}/CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO{sub 2} and CH{sub 4}. In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH{sub 4} direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH{sub 4} dehydrogenation on Pt(1 1 1) surface. In the process of CO{sub 2} activation, three possible reaction pathways are considered to contribute to the CO{sub 2} decomposition: (I) CO{sub 2}* + * → CO* + O*; (II) CO{sub 2}* + H* → COOH* + * → CO* + OH*; (III) CO{sub 2}* + H* → mono-HCOO* + * → bi-HCOO* + * [CO{sub 2}* + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In

  3. Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

    KAUST Repository

    Biausque, Gregory

    2015-04-28

    Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

  4. Partial and Total Oxidation of Methane in Monolithic Catalysts at Short Contact Times

    OpenAIRE

    Schwiedernoch, Renate

    2005-01-01

    The feedstocks of natural gas exceed the resources of crude oil by far. Therefore, there is a strong interest in the utilisation of natural gas with its main component methane for the production of more useful chemicals. This leads to a strong demand for compact and low-capital-cost reactors for the conversion of natural gas to methanol and liquid hydrocarbons and the production of H2. The combustion of natural gas is also considered for power generation in catalytic devices, because the flam...

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

    Energy Technology Data Exchange (ETDEWEB)

    S Senanayake; J Evans; S Agnoli; L Barrio; T Chen; J Hrbek; J Rodriguez

    2011-12-31

    X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO{sub 2}(111) surfaces. Upon adsorption on CeO{sub 2}(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500-800 K) leads to partial reduction of the ceria substrate with the formation of Ni{sup 2+} species that exists as NiO and/or Ce{sub 1-x}Ni{sub x}O{sub 2-y}. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO{sub 2}(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce{sup +3} cations, CO dissociates on the surface at 300 K forming NiC{sub x} compounds that may be involved in the formation of CH{sub 4} at higher temperatures. At medium and large Ni coverages (>0.3 ML), the Ni/CeO{sub 2}(111) surfaces are able to catalyze the production of methane from CO and H{sub 2}, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (<0.3 ML), the Ni/CeO{sub 2}(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water-gas shift reaction.

  6. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst

    Directory of Open Access Journals (Sweden)

    New Pei Yee

    2008-04-01

    Full Text Available A one-dimensional mathematical model was developed to simulate the performance of catalytic fixed bedreactor for carbon dioxide reforming of methane over Rh/Al2O3 catalyst at atmospheric pressure. The reactionsinvolved in the system are carbon dioxide reforming of methane (CORM and reverse water gas shiftreaction (RWGS. The profiles of CH4 and CO2 conversions, CO and H2 yields, molar flow rate and molefraction of all species as well as reactor temperature along the axial bed of catalyst were simulated. In addition,the effects of different reactor temperature on the reactor performance were also studied. The modelscan also be applied to analyze the performances of lab-scale micro reactor as well as pilot-plant scale reactorwith certain modifications and model verification with experimental data. © 2008 BCREC UNDIP. All rights reserved.[Received: 20 August 2008; Accepted: 25 September 2008][How to Cite: N.A.S. Amin, I. Istadi, N.P. Yee. (2008. Mathematical Modelling of Catalytic Fixed-Bed Reactor for Carbon Dioxide Reforming of Methane over Rh/Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering and Catalysis, 3 (1-3: 21-29. doi:10.9767/bcrec.3.1-3.19.21-29

  7. Structured catalysts for methane auto-thermal reforming in a compact thermal integrated reaction system

    International Nuclear Information System (INIS)

    Palma, Vincenzo; Ricca, Antonio; Ciambelli, Paolo

    2013-01-01

    In this work a compact catalytic reactor was analysed for the ATR of CH 4 as natural gas surrogate. Structured catalysts (commercial honeycomb and foam monoliths) performances in CH 4 processing were studied. In reactor design, great attention has been paid to the thermal integration, in order to obtain a total self-sustainability of the process avoiding additional external heat sources, and improving the plant compactness. Through a heat exchange system integrated in the reactor, water and air streams are preheated by exploiting the heat from exhaust stream, allowing to feed reactants at room temperature as well as cooling products stream at a temperature suitable for further purification stages (Water Gas Shift, Preferential Oxidation). In order to have a very comprehensive process analysis, temperatures and composition were monitored in 6 point along the catalytic bed. The influence of catalytic system geometry and thermal conductivity in the process performances were also analysed. Preliminary tests showed high thermal system efficiency, with a good hydrocarbon conversion at different operating conditions for both catalyst typologies

  8. Molecularly Tailored Nickel Precursor and Support Yield a Stable Methane Dry Reforming Catalyst with Superior Metal Utilization.

    Science.gov (United States)

    Margossian, Tigran; Larmier, Kim; Kim, Sung Min; Krumeich, Frank; Fedorov, Alexey; Chen, Peter; Müller, Christoph R; Copéret, Christophe

    2017-05-24

    Syngas production via the dry reforming of methane (DRM) is a highly endothermic process conducted under harsh conditions; hence, the main difficulty resides in generating stable catalysts. This can, in principle, be achieved by reducing coke formation, sintering, and loss of metal through diffusion in the support. [{Ni(μ 2 -OCHO)(OCHO)(tmeda)} 2 (μ 2 -OH 2 )] (tmeda = tetramethylethylenediamine), readily synthesized and soluble in a broad range of solvents, was developed as a molecular precursor to form 2 nm Ni(0) nanoparticles on alumina, the commonly used support in DRM. While such small nanoparticles prevent coke deposition and increase the initial activity, operando X-ray Absorption Near-Edge Structure (XANES) spectroscopy confirms that deactivation largely occurs through the migration of Ni into the support. However, we show that Ni loss into the support can be mitigated through the Mg-doping of alumina, thereby increasing significantly the stability for DRM. The superior performance of our catalytic system is a direct consequence of the molecular design of the metal precursor and the support, resulting in a maximization of the amount of accessible metallic nickel in the form of small nanoparticles while preventing coke deposition.

  9. Methane dry reforming over Ni catalysts supported on Ce–Zr oxides prepared by a route involving supercritical fluids

    Directory of Open Access Journals (Sweden)

    Smirnova Marina Yu.

    2017-12-01

    Full Text Available Ce0.5Zr0.5O2 mixed oxides were prepared in a flow reactor in supercritical isopropanol with acetylacetone as a complexing agent. Variation of the nature of the Zr salt and the temperature of synthesis affected the phase composition, morphology and specific surface area of oxides. X-ray diffraction and Raman spectroscopy studies revealed formation of metastable t” and t’ phases. Oxides are comprised of agglomerates with sizes depending on the synthesis parameters. Loading NiO decreases the specific surface area without affecting X-ray particle sizes of supports. Such sintering was the most pronounced for a support with the highest specific surface area, which resulted in the lowest surface content of Ni as estimated by X-ray photoelectron spectroscopy and in the formation of flattened NiO particles partially embedded into the support. The catalytic activity and stability of these samples in the dry reforming of methane were determined by the surface concentration of Ni and the morphology of its particle controlled by the metal-support interaction, which also depends on the type of catalyst pretreatment. Samples based on ceria-zirconia oxides prepared under these conditions provide a higher specific catalytic activity as compared with the traditional Pechini route, which makes them promising for the practical application.

  10. Hydrogen production by dry reforming of methane with carbon dioxide in one-dimensional nickel-based catalysts; Produccion de hidrogeno mediante el reformado seco de metano con dioxido de carbono en catalizadores unidimensionales a base de niquel

    Energy Technology Data Exchange (ETDEWEB)

    Lopez U, A. C.

    2016-07-01

    The main objective of this thesis is development of nickel catalysts supported over 1D matrix of cerium oxide, to be used in dry reforming methane reaction with carbon dioxide for hydrogen production. The catalysts were characterized by: Temperature Programmed Reduction (TPR), Scanning Electronic Microscopy (Sem), Surface Area (Bet method) an X Ray Diffraction (XRD). The TPR technique allowed to define reduction temperature of the active phase in the catalyst, Sem technique showed that the CeO{sub 2} matrix had a nano rod morphology. XRD allowed to identify the crystalline phases of the catalysts. Finally, the catalysts were tested in the dry reforming methane reaction, high catalytic activity and hydrogen production were performed at 700 degrees Celsius and the catalyst with 30 wt.% of nickel. (Author)

  11. Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy.

    Science.gov (United States)

    Eilert, André; Roberts, F Sloan; Friebel, Daniel; Nilsson, Anders

    2016-04-21

    Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)-carbonate/hydroxide is also reported. This study highlights the importance of using oxidized copper precursors for constructing selective CO2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.

  12. Optimization of process parameters and catalyst compositions in carbon dioxide oxidative coupling of methane over CaO-MnO/CeO{sub 2} catalyst using response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Istadi,; Amin, Nor Aishah Saidina [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, UTM Skudai, Johor Bahru (81310 Malaysia)

    2006-05-15

    The optimization of process parameters and catalyst compositions for the CO{sub 2} oxidative coupling of methane (CO{sub 2}-OCM) reaction over CaO-MnO/CeO{sub 2} catalyst was developed using Response Surface Methodology (RSM). The relationship between the responses, i.e. CH{sub 4} conversion, C{sub 2} hydrocarbons selectivity or yield, with four independent variables, i.e. CO{sub 2}/CH{sub 4} ratio, reactor temperature, wt.% CaO and wt.% MnO in the catalyst, were presented as empirical mathematical models. The maximum C{sub 2} hydrocarbons selectivity and yields of 82.62% and 3.93%, respectively, were achieved by the individual-response optimization at the corresponding optimal process parameters and catalyst compositions. However, the CH{sub 4} conversion was a saddle function and did not show a unique optimum as revealed by the canonical analysis. Moreover pertaining to simultaneous multi-responses optimization, the maximum C{sub 2} selectivity and yield of 76.56% and 3.74%, respectively, were obtained at a unique optimal process parameters and catalyst compositions. It may be deduced that both individual- and multi-responses optimizations are useful for the recommendation of optimal process parameters and catalyst compositions for the CO{sub 2}-OCM process. (author)

  13. An electron microscopy study of catalysts for the production of hydrogen cyanide by the ammoxidation of methane

    International Nuclear Information System (INIS)

    Hutchings, G.J.

    1985-01-01

    An electron microscopy study of Andrussow-process catalysts, based on platinum supported on beryl, is reported. The number of platinum impregnation stages in the catalyst preparation is found to significantly affect the platinum coverage. Electron micrographs of unused and used catalysts are compared with those of similar studies previously published for platinum gauze catalyst. In addition, the levels of known catalyst poisons, namely iron and nickel, are studied

  14. A novel continuous process for synthesis of carbon nanotubes using iron floating catalyst and MgO particles for CVD of methane in a fluidized bed reactor

    Energy Technology Data Exchange (ETDEWEB)

    Maghsoodi, Sarah; Khodadadi, Abasali [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: mortazav@ut.ac.ir [Nanoelectronics Centre of Excellence, University of Tehran, POB 11365-4563, Tehran (Iran, Islamic Republic of)

    2010-02-15

    A novel continuous process is used for production of carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CVD) of methane on iron floating catalyst in situ deposited on MgO in a fluidized bed reactor. In the hot zone of the reactor, sublimed ferrocene vapors were contacted with MgO powder fluidized by methane feed to produce Fe/MgO catalyst in situ. An annular tube was used to enhance the ferrocene and MgO contacting efficiency. Multi-wall as well as single-wall CNTs was grown on the Fe/MgO catalyst while falling down the reactor. The CNTs were continuously collected at the bottom of the reactor, only when MgO powder was used. The annular tube enhanced the contacting efficiency and improved both the quality and quantity of CNTs. The SEM and TEM micrographs of the products reveal that the CNTs are mostly entangled bundles with diameters of about 10-20 nm. Raman spectra show that the CNTs have low amount of amorphous/defected carbon with I{sub G}/I{sub D} ratios as high as 10.2 for synthesis at 900 deg. C. The RBM Raman peaks indicate formation of single-walled carbon nanotubes (SWNTs) of 1.0-1.2 nm diameter.

  15. Enhanced gasification of wood in the presence of mixed catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Weber, S. L.; Mudge, L. K.; Sealock, Jr., L. J.; Robertus, R. J.; Mitchell, D. E.

    Experimental results obtained in laboratory investigations of steam gasification of wood in the presence of mixed catalysts are presented. These studies are designed to test the technical feasibility of producing specific gaseous products from wood by enhancing its reactivity and product specificity through the use of combined catalysts. The desired products include substitute natural gas, hydrocarbon synthesis gas and ammonia synthesis gas. The gasification reactions are controlled through the use of specific catalyst combinations and operating parameters. A primary alkali carbonate gasification catalyst impregnated into the wood combined with specific commercially available secondary catalysts produced the desired products. A yield of 50 vol % methane was obtained with a randomly mixed combination of a commercial nickel methanation catalyst and silica-alumina cracking catalyst at a weight ratio of 3:1 respectively. Steam gasification of wood in the presence of a commercial Si-Al cracking catalyst produced the desired hydrocarbon synthesis gas. Hydrogen-to-carbon monoxide ratios needed for Fischer-Tropsch synthesis of hydrocarbons were obtained with this catalyst system. A hydrogen-to-nitrogen ratio of 3:1 for ammonia synthesis gas was achieved with steam-air gasification of wood in the presence of catalysts. The most effective secondary catalyst system employed to produce the ammonia synthesis gas included two commercially prepared catalysts formulated to promote the water-gas shift reaction.

  16. Comparative study on cubic and tetragonal CexZr1-xO2 supported MoO3-catalysts for sulfur-resistant methanation

    Science.gov (United States)

    Liu, Zhaopeng; Xu, Yan; Cheng, Jiaming; Wang, Weihan; Wang, Baowei; Li, Zhenhua; Ma, Xinbin

    2018-03-01

    In this paper, two kinds of CexZr1-xO2 solid solution carriers with different Ce/Zr ratio were prepared by one-step co-precipitation method: the cubic Ce0.8Zr0.2O2 and the tetragonal Ce0.2Zr0.8O2 support. The MoO3/Ce0.8Zr0.2O2 and MoO3/Ce0.2Zr0.8O2 catalysts were prepared by incipient wetness impregnation method for comparative study on sulfur-resistant methanation reaction. The N2 adsorption/desorption, X-ray diffraction (XRD), Raman spectroscopy (RS), X-ray photoelectron (XPS), transmission electron microscopy (TEM), temperature-programmed reduction by hydrogen (H2-TPR) were undertaken to characterize the physico-chemical properties of the samples. The results indicated that the prepared MoO3/CexZr1-xO2 catalysts have a mesoporous structure with high surface area and uniform pore size distribution, achieving good MoO3 dispersion on CexZr1-xO2 supports. As for the catalytic performance of sulfur-resistant methanation, the cubic MoO3/Ce0.8Zr0.2O2 exhibited better than the tetragonal MoO3/Ce0.2Zr0.8O2 catalyst at reaction temperature 400 °C and 450 °C. CO conversion on the cubic MoO3/Ce0.8Zr0.2O2 catalyst was 50.1% at 400 °C and 75.5% at 450 °C, which is respectively 7% and 20% higher than that on the tetragonal MoO3/Ce0.2Zr0.8O2 catalyst. These were mainly attributed to higher content of active MoS2 on the surface of catalyst, the enhanced oxygen mobility, increased Mo-species dispersion as well as the excellent reducibility resulted from the increased amount of the reducible Ce3+ on the cubic MoO3/Ce0.8Zr0.2O2 catalyst.

  17. Catalytic reduction of SO{sub 2} with methane over molybdenum catalyst. Quarterly report, 1 December 1994--28 February 1995

    Energy Technology Data Exchange (ETDEWEB)

    Wiltowski, T.

    1995-12-31

    One of the primary concerns in coal utilization is the emission of sulfur compounds, especially SO{sub 2}. This project deals with catalytic reduction of SO{sub 2} with methane using molybdenum sulfide catalyst supported on different activated carbons: Darco TRS, Norit ROZ-3, and an activated carbon prepared from Illinois coal IBC-110. The work conducted during this quarter has concentrated on continuation of the synthesis of activated carbon derived from Illinois coal IBC-110, modification and improvement of the apparatus for the catalyst testing, ESCA (XPS) analysis of the catalyst (10% MoS{sub 2} on Darco TRS activated carbon), and experiments in the temperature range of 450{degree}C--600{degree}C for the S0{sub 2}:CH{sub 4} ratio equal 1:1. XPS study confirmed that Mo is present in the form of Mo+4 and S in the form of S-2. The catalytic experiments of SO{sub 2} reduction with CH{sub 4} showed that for both Darco TRS and ROZ-3 supports, S0{sub 2} conversion increases with the temperature. Also, the catalyst having 20% loading of MoS{sub 2} on Darco TRS support shows the highest S0{sub 2} conversion over 10% or 15% loadings on Darco TRS. In contrast, for the ROZ-3 support, the catalyst having a 15% loading shows the highest activity. Additionally, it was observed that conversions of S0{sub 2} at 600{degree}C for both supports are comparable to each other when catalysts with 20% loadings are used; at lower temperatures, the activities are quite different with the conversions being higher for Darco TRS support.

  18. Ni/SiO2 Catalyst Prepared with Nickel Nitrate Precursor for Combination of CO2 Reforming and Partial Oxidation of Methane: Characterization and Deactivation Mechanism Investigation

    Directory of Open Access Journals (Sweden)

    Sufang He

    2015-01-01

    Full Text Available The performance of Ni/SiO2 catalyst in the process of combination of CO2 reforming and partial oxidation of methane to produce syngas was studied. The Ni/SiO2 catalysts were prepared by using incipient wetness impregnation method with nickel nitrate as a precursor and characterized by FT-IR, TG-DTA, UV-Raman, XRD, TEM, and H2-TPR. The metal nickel particles with the average size of 37.5 nm were highly dispersed over the catalyst, while the interaction between nickel particles and SiO2 support is relatively weak. The weak NiO-SiO2 interaction disappeared after repeating oxidation-reduction-oxidation in the fluidized bed reactor at 700°C, which resulted in the sintering of metal nickel particles. As a result, a rapid deactivation of the Ni/SiO2 catalysts was observed in 2.5 h reaction on stream.

  19. Axial Changes of Catalyst Structure and Temperature in a Fixed-Bed Microreactor During Noble Metal Catalysed Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Hannemann, S.; Grunwaldt, Jan-Dierk; Kimmerle, B.

    2009-01-01

    The catalytic partial oxidation of methane (CPO) over flame-made 2.5%Rh-2.5%Pt/Al2O3 and 2.5%Rh/Al2O3 in 6%CH4/3%O-2/He shows the potential of in situ studies using miniaturized fixed-bed reactors, the importance of spatially resolved studies and its combination with infrared thermography and on......-line mass spectrometry. This experimental strategy allowed collecting data on the structure of the noble metal (oxidation state) and the temperature along the catalyst bed. The reaction was investigated in a fixed-bed quartz microreactor (1-1.5 mm diameter) following the catalytic performance by on-line gas...... mass spectrometry (MS). Above the ignition temperature of the catalytic partial oxidation of methane (310-330 A degrees C), a zone with oxidized noble metals was observed in the inlet region of the catalyst bed, accompanied by a characteristic hot spot (over-temperature up to 150 A degrees C), while...

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

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., (United States); Gutterman, C. [Foster Wheeler Development Corp., Livingston, NJ (United States); Chander, S. [Pennsylvania State Univ., (United States)

    1994-12-31

    The overall objective of this project was to develop a new approach for the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrated coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. Heterofunctional solvents were the most effective in swelling coals. Also solvent blends such as isopropanol/water were more effective than pure solvents alone. Impregnating slurry catalysts simultaneously during coal swelling showed that better uptake was achieved with nonswelling solvent and higher impregnation temperature. Some enhancement in initial coal conversion was seen liquefying SO{sub 2}-treated Black Thunder coal with slurry catalysts, and also when hydrogen donor liquefaction solvents were used. Noncatalytic reactions showed no benefit from SO{sub 2} treatment. Coupling coal swelling and SO{sub 2} treatment with slurry catalysts was also not beneficial, although high conversion was seen with continuous operation and long residence time, however, similar high conversion was observed with untreated coal. SO{sub 2} treatment is not economically attractive unless it provides about 17% increase in coal reactivity. In most cases, the best results were obtained when the coal was untreated and the slurry catalyst was added directly into the reactor. Foster Wheeler`s ASCOT process had better average liquid yields than either Wilsonville`s vacuum tower/ROSE combination or delayed coking process. This liquid product also had good quality.

  1. Self-Assembled Pd@CeO2/γ-Al2O3Catalysts with Enhanced Activity for Catalytic Methane Combustion.

    Science.gov (United States)

    Feng, Xilan; Li, Wang; Liu, Dapeng; Zhang, Zheng; Duan, Yang; Zhang, Yu

    2017-08-01

    Pd@CeO 2 /Al 2 O 3 catalysts are of great importance for real applications, such as three-way catalysis, CO oxidation, and methane combustion. In this article, the Pd@CeO 2 core@shell nanospheres are prepared via the autoredox reaction in aqueous phase. Three kinds of methods are then employed, that is, electrostatic interaction, supramolecular self-assembly, and physical mixing, to support the as-prepared Pd@CeO 2 nanospheres on γ-Al 2 O 3 . A model reaction of catalytic methane-combustion is employed here to evaluate the three Pd@CeO 2 /γ-Al 2 O 3 samples. As a result, the sample Pd@CeO 2 -S-850 prepared via supramolecular self-assembly and calcined at 850 °C exhibits superior catalytic performance to the others, which has a far lower light-off temperature (T 50 of about 364 °C). Moreover, almost no deterioration of Pd@CeO 2 -S-850 is observed after five sequent catalytic cycles. The analysis of H 2 -TPR curves concludes that there exists hydrogen spillover related to the strong metal-support interaction between Pd species and oxides. The strong metal-support interaction and the specific surface areas might be responsible for the catalytic performance of the Pd@CeO 2 samples toward catalytic methane combustion. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A DFT study of Ru, Rh, Pd, Os, Ir, and Pt clusters as catalysts for methane dissociation in a direct methane fuel cell (DMHFC)

    Energy Technology Data Exchange (ETDEWEB)

    Psofogiannakisa, G. [Ottawa Univ., Ottawa, ON (Canada). Dept. of Chemical Engineering; Ottawa, Univ., Ottawa, ON (Canada). Centre for Catalysis Research and Innovation; St-Amant, A. [Ottawa Univ., Ottawa, ON (Canada). Dept. of Chemistry; Ternan, M. [Ottawa Univ., Ottawa, ON (Canada). Centre for Catalysis Research and Innovation; EnPross Inc., Ottawa, ON (Canada)

    2008-07-01

    The rate limiting step in a direct methane hydrocarbon fuel cell (DMHFC) is the dissociative chemisorption of methane. Quantum mechanical computations were used to examine the terrace, kink, and step sites on 6 different clusters of group 8 transition metals, notably Ru, Rh, Pd, Os, Ir, and Pt. The computations involved the anodic reaction of a DMHFC with a polymer electrolyte that operates at atmospheric pressure and temperatures higher than 120 degrees C. The interaction between molecular fragments and a surface (Pt) were described and density functional theory (DFT) calculations were performed using Guassian software. The geometries of 5 different platinum clusters were examined along with their electronic energy barriers. The biggest contribution to the stabilization energy came from the overlap between the sigma bond in methane and unoccupied sd hybrid orbitals in the Pt bonding atom. The study showed that when relaxation was allowed, the displacement of the bonding metal atom was 0.36 to 0.52 A. The electronic energy barrier often increased as d-orbital occupancy increased. For the kink surface sites, the energy barriers were considerably smaller for the 5d transition metals than for the 4d transition metals. 5 refs., 1 tab.

  3. The Impact of Ce-Zr Addition on Nickel Dispersion and Catalytic Behavior for CO2 Methanation of Ni/AC Catalyst at Low Temperature

    Directory of Open Access Journals (Sweden)

    Minh Cam Le

    2017-01-01

    Full Text Available The CO2 methanation was studied over 7 wt.% nickel supported on Ce0.2Zr0.8O2/AC to evaluate the correlation of the structural properties with catalytic performance. The catalysts were investigated in more detail by means of X-ray diffraction (XRD, transmission electron microscopy (TEM, and scanning electron microscopy (SEM. A sample of 7 wt.% nickel loading supported on activated carbon (AC was also prepared for comparison. The results demonstrated that the ceria-zirconia solid solution phase could disperse and stabilize the nickel species more effectively and resulted in stronger interaction with nickel than the parent activated carbon phase. Therefore, 7% Ni/Ce0.2Zr0.8O2/AC catalyst exhibited higher activity for CO2 reduction than 7% Ni//AC. It can attain 85% CO2 conversion at 350°C and have a CH4 selectivity of 100% at a pressure as low as 1 atm. The high activity of prepared catalysts is attributed to the good interaction between Ni and Ce0.2Zr0.8O2 and the high CO2 adsorption capacity of the activated carbon as well.

  4. Simultaneous oxidative conversion and co/sub 2/ reforming of methane to syngas over modified Ni/Al/sub 2/O/sub 3/ catalysts

    International Nuclear Information System (INIS)

    Eli, W.

    2013-01-01

    A series of Ni/Al/sub 2/O/sub 3/ and modified Ni-M/Al/sub 2/O/sub 3/ (MLa, Na, K, Ca and Ba) catalysts have been prepared and characterized by XRD, BET, XPS, TGA, TEM and SEM. The performance of these catalysts for simultaneous oxidative conversion and CO/sub 2/ reforming of methane to syngas was evaluated using a fixed-bed reactor. The results indicated that the catalytic activity of Ni/Al/sub 2/O/sub 3/ increased with Ni loading, and reached maximum at 12% Ni loading. The La-modified Ni/Al/sub 2/O/sub 3/ exhibited an excellent catalytic activity and stability within 20 h as compared with unmodified and Na-modified ones. It was found that the addition of La decreased the particle size of nickel, thus increased the Ni dispersion accordingly as indicated by the characterization data. The catalytic activity of Na-modified Ni/Al/sub 2/O/sub 3/ decreased obviously only after 6 h of reaction due to aggregation of metallic Ni particles. Hence, it was suggested that the sintering of Ni particles dominated the catalyst deactivation during the catalytic reaction process. (author)

  5. Simple cerium-triethanolamine complex: Synthesis, characterization, thermal decomposition and its application to prepare ceria support for platinum catalysts used in methane steam reforming

    Science.gov (United States)

    Wattanathana, Worawat; Nootsuwan, Nollapan; Veranitisagul, Chatchai; Koonsaeng, Nattamon; Laosiripojana, Navadol; Laobuthee, Apirat

    2015-06-01

    Cerium-triethanolamine complex was synthesized by simple complexation method in 1-propanol solvent using cerium(III) chloride as a metal source and triethanolamine as a ligand. The structures of the prepared complex were proposed based on FT-IR, FT-Raman and ESI-MS results as equimolar of triethanolamine and cerium chelated complex having monomeric tricyclic structure with and without chloride anion as another coordinating group known as ceratrane. The complex was used as a precursor for ceria material done by thermal decomposition. XRD result revealed that when calcined at 600 °C for 2 h, the cerium complex was totally turned into pure ceria with cubic fluorite structure. The obtained ceria was then employed to synthesize platinum doped ceria catalysts for methane steam reforming. Various amounts of platinum i.e. 1, 3, 5 and 10 mol percents were introduced on the ceria support by microwave-assisted wetness impregnation using ammonium tetrachloroplatinate(II). The platinum-impregnated ceria powders were subjected to calcination in 10% hydrogen/helium atmosphere at 500 °C for 3 h to reduce platinum(II) to platinum(0). XRD patterns of the catalysts confirmed that the platinum particles doped on the ceria support were in the form of platinum(0). Catalytic activity test showed that the catalytic activities got higher as the amounts of platinum doped increased. Besides, the portions of coke formation on the surface of catalysts were reduced as the amounts of platinum doped increased.

  6. Flexibilization of methanization units in Germany. Overview of technical approaches, of the regulatory framework, and of the importance for the energy system - Synthesis note

    International Nuclear Information System (INIS)

    Trommler, Marcus; Dotzauer, Martin; Barchmann, Tino; Lauer, Markus; Hennig, Christiane; Mauky, Eric; Liebetrau, Jan; Thraen, Daniela; Risler, Julian

    2016-03-01

    Technologies of valorisation of biomass offer opportunities to produce a flexible and renewable energy suitable to compensate the intermittency of wind and solar energies which depend on meteorological conditions. As methanization units operated in a flexible way are now mainly present in Germany, notably due to public financial supports to flexibility, this publication describes the status of flexibilization in German methanization units, and highlights relationships with the electricity system, technical approaches to flexibility (implemented technology, gas valorisation in biomethane and injection in the natural gas network, adjustment of gas production for supply management, methanization units and hybrid concepts), and incentive policy (flexibility premium, marketing strategy). The publication finally discusses perspectives for these flexible methanization units

  7. Final Scientific/Technical Report. A closed path methane and water vapor gas analyzer

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Liukang [LI-COR Inc., Lincoln, NE (United States); McDermitt, Dayle [LI-COR Inc., Lincoln, NE (United States); Anderson, Tyler [LI-COR Inc., Lincoln, NE (United States); Riensche, Brad [LI-COR Inc., Lincoln, NE (United States); Komissarov, Anatoly [LI-COR Inc., Lincoln, NE (United States); Howe, Julie [LI-COR Inc., Lincoln, NE (United States)

    2012-02-01

    Robust, economical, low-power and reliable closed-path methane (CH4), carbon dioxide (CO2), and water vapor (H2O) analyzers suitable for long-term measurements are not readily available commercially. Such analyzers are essential for quantifying the amount of CH4 and CO2 released from various ecosystems (wetlands, rice paddies, forests, etc.) and other surface contexts (e.g. landfills, animal husbandry lots, etc.), and for understanding the dynamics of the atmospheric CH4 and CO2 budget and their impact on climate change and global warming. The purpose of this project is to develop a closed-path methane, carbon dioxide gas and water vapor analyzer capable of long-term measurements in remote areas for global climate change and environmental research. The analyzer will be capable of being deployed over a wide range of ecosystems to understand methane and carbon dioxide exchange between the atmosphere and the surface. Measurements of methane and carbon dioxide exchange need to be made all year-round with limited maintenance requirements. During this Phase II effort, we successfully completed the design of the electronics, optical bench, trace gas detection method and mechanical infrastructure. We are using the technologies of two vertical cavity surface emitting lasers, a multiple-pass Herriott optical cell, wavelength modulation spectroscopy and direct absorption to measure methane, carbon dioxide, and water vapor. We also have designed the instrument application software, Field Programmable Gate Array (FPGA), along with partial completion of the embedded software. The optical bench has been tested in a lab setting with very good results. Major sources of optical noise have been identified and through design, the optical noise floor is approaching -60dB. Both laser modules can be temperature controlled to help maximize the stability of the analyzer. Additionally, a piezo electric transducer has been

  8. Electrical conductivity of lab-formed methane hydrate + sand mixtures; technical developments and new results

    Science.gov (United States)

    Stern, L.; Du Frane, W. L.; Weitemeyer, K. A.; Constable, S.; Roberts, J. J.

    2012-12-01

    Electromagnetic (EM) measurement techniques used in permafrost and marine wells show that electrical conductivity (σ) of gas-hydrate-bearing zones is typically lower than that of surrounding sediments. However, while σ has been measured on analogue materials, it has seldom been studied on methane hydrate, the most common gas hydrate in the shallow geosphere. Additional petrophysical information - such as mixing relations and/or compositions of individual components - is also needed to more accurately relate σ to quantitative estimates of gas hydrate in EM-surveyed regions. To help address these needs, we first quantified the electrical properties of lab-formed methane hydrate at geologically relevant temperatures and pressures (Du Frane et al. GRL, 2011; also AGU 2011). A high-pressure cell was constructed to form hydrate from melting granular ice (made from distilled-deionized water) in the presence of pressurized CH4 gas, while measuring frequency-dependent impedance (Z) and σ. Final samples were pure, polycrystalline methane hydrate with excess CH4 gas but no excess H2O. The hydrate was then either quenched for grain-scale assessment by cryogenic SEM imaging, or dissociated in situ for further Z and σ measurement. Du Frane et al. [GRL, 2011] reported σ of methane hydrate to range from 10-5 to 10-4 S/m between -15 and 15°C, with activation energy (Ea) of 30.6 kJ/mol. In comparison, σ of the dissociated ice byproduct was ~400% higher with ~50% higher Ea. Measurements were then performed on methane hydrate mixed with known amounts of a standard quartz sand (Oklahoma #1, ~125 μm grain size) or similarly-sized silica glass beads in proportions ranging 10 to 90 vol. % relative to the hydrate phase. Several samples were dissociated at temperatures below -3°C for Z and σ measurement of the resulting ice/sand mixtures, and all samples were imaged for phase distribution. Adding sand complicated Z spectra for frequencies 1MHz. However, the impedance at the

  9. La2O3/CaO CATALYSTS AND ITS APPLICATION IN THE OXIDATIVE COUPLING OF METHANE

    OpenAIRE

    Garrido-Schaeffer, A.; Dedios Yenque, G.; Ponce Alvaréz, S.

    2014-01-01

    La2O3/CaO catalysts were prepared at different weight percentages of La2O3.Por the coprecipitation method described porRaO, CaCO3 is prepared and then it was impregnated in a solution of La (NO) 3.6H2O thus obtaining the catalyst precursor . precursors dried at 393K and calcined at 973K, obtaining 0-15% La2O3/CaO catalysts. XRF elemental qualitative analysis was performed. By FTIR carbonates adsorbed species was observed. The presence of La2O3 and CaO phases was confirmed by XRD and BET surfa...

  10. Methyl chloride via oxyhydrochlorination of methane. Quarterly technical progress report No. 5, October--December 1992

    Energy Technology Data Exchange (ETDEWEB)

    1993-06-01

    Objective is to develop a process for converting light alkane gases to methyl chloride via oxyhydrochlorination using highly selective, stable catalysts (CuO based) in fixed-bed reactors designed to remove the large amount of heat generated, so as to control the reaction temperature. The proposed PFD for this unit was described to management, and the PDU PFD is currently being expanded into a P&ID with a subcontractor.

  11. Nickel catalyst supported on magnesium and zinc aluminates (MgAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4}) spinels for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, L.C.B. de; Melo, D.M. de A.; Melo, M.A. de F.; Barros, J.M. de F.; Braga, R.M.; Costa, C. de C.; Rodrigues, G., E-mail: ieda.garcia@pq.cnpq.br [Universidade Federal da Paraiba (LACOM/UFPB), Joao Pessoa, PB (Brazil). Dept. de Quimica

    2017-01-15

    Materials such as MgAl{sub 2}O{sub 4} and ZnAl{sub 2}O{sub 4} assessed in the reaction of dry reforming of methane to produce syngas were synthesized by microwave-assisted combustion method using urea as fuel. Samples of synthesized oxides were calcined at 800 °C for 2 h and impregnated with 5% nickel. The impregnated samples were calcined at 850 °C for 4 h to obtain the desired phases. The results of the catalytic tests showed that the catalysts are active for the reaction of dry reforming of methane, and the catalyst that showed the best performance for methane conversion was 5% Ni/MgAl{sub 2}O{sub 4} calcined at 850 °C/4 h. (author)

  12. Steam reforming of methane over Pt/Rh based wire mesh catalyst in single channel reformer for small scale syngas production

    DEFF Research Database (Denmark)

    Sigurdsson, Haftor Örn; Kær, Søren Knudsen

    2012-01-01

    of a catalytic parallel plate type heat exchanger (CPHE) reformer stack, where coated Pt/Rh based wire mesh is used as a catalyst. Heat is supplied to the endothermic reaction with infrared electric heaters. All the experiments were performed under atmospheric pressure and at stable operating conditions......The purpose of this study is to investigate a small scale steam methane reformer for syngas production for a micro combined heat and power (mCPH) unit under different operational conditions. The study presents an experimental analysis of the performance of a specially built single channel...... to evaluate the effect of flow maldistribution in a CPHE reformer stack on the CH4 conversion and H2 yield....

  13. Production of methane-rich syngas from hydrocarbon fuels using multi-functional catalyst/capture agent

    Energy Technology Data Exchange (ETDEWEB)

    Siefert, Nicholas S; Shekhawat, Dushyant; Berry, David A; Surdoval, Wayne A

    2014-12-30

    The disclosure provides a gasification process for the production of a methane-rich syngas at temperatures exceeding 700.degree. C. through the use of an alkali hydroxide MOH, using a gasification mixture comprised of at least 0.25 moles and less than 2 moles of water for each mole of carbon, and at least 0.15 moles and less than 2 moles of alkali hydroxide MOH for each mole of carbon. These relative amounts allow the production of a methane-rich syngas at temperatures exceeding 700.degree. C. by enabling a series of reactions which generate H.sub.2 and CH.sub.4, and mitigate the reforming of methane. The process provides a methane-rich syngas comprised of roughly 20% (dry molar percentage) CH.sub.4 at temperatures above 700.degree. C., and may effectively operate within an IGFC cycle at reactor temperatures between 700-900.degree. C. and pressures in excess of 10 atmospheres.

  14. A novel study of methane-rich gas reforming to syngas and its kinetics over semicoke catalyst.

    Science.gov (United States)

    Zhang, Guojie; Su, Aiting; Qu, Jiangwen; Du, Yannian

    2014-01-01

    A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: [Formula in text].

  15. A Novel Study of Methane-Rich Gas Reforming to Syngas and Its Kinetics over Semicoke Catalyst

    Directory of Open Access Journals (Sweden)

    Guojie Zhang

    2014-01-01

    Full Text Available A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: k-=5.02×103·pCH40.71·pH20.26·exp(−74200/RT.

  16. Effect of addition of a second metal in Mo/ZSM-5 catalyst for methane aromatization reaction under elevated pressures

    Czech Academy of Sciences Publication Activity Database

    Fíla, V.; Bernauer, Milan; Bernauer, B.; Sobalík, Zdeněk

    2015-01-01

    Roč. 256, č. 2 (2015), s. 269-275 ISSN 0920-5861 Grant - others:EU 7th Framework Program(XE) NMP3-LA-2009-229183 Institutional support: RVO:61388955 Keywords : methane * aromatization * metal dopants Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.312, year: 2015

  17. A Novel Study of Methane-Rich Gas Reforming to Syngas and Its Kinetics over Semicoke Catalyst

    Science.gov (United States)

    Zhang, Guojie; Su, Aiting; Qu, Jiangwen; Du, Yannian

    2014-01-01

    A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: k-=5.02×103·pCH40.71·pH20.26·exp(−74200/RT). PMID:24959620

  18. Catalytic Chemical Vapor Deposition of Methane to Carbon Nanotubes: Copper Promoted Effect of Ni/MgO Catalysts

    Directory of Open Access Journals (Sweden)

    Wen Yang

    2014-01-01

    Full Text Available The Ni/MgO and Ni-Cu/MgO catalysts were prepared by sol-gel method and used as the catalysts for synthesis of carbon nanotubes by thermal chemical vapor deposition. The effect of Cu on the carbon yield and structure was investigated, and the effects of calcination temperature and reaction temperature were also investigated. The catalysts and synthesized carbon materials were characterized by temperature programmed reduction (TPR, thermogravimetric analysis (TGA, and scanning electron microscopy (SEM. Results showed that the addition of Cu promoted the reduction of nickel species, subsequently improving the growth and yield of CNTs. Meanwhile, CNTs were synthesized by the Ni/MgO and Ni-Cu/MgO catalysts with various calcination temperatures and reaction temperatures, and results suggested that the obtained CNTs on Ni-Cu/MgO catalyst with the calcination temperature of 500°C and the reaction temperature of 650°C were of the greatest yield and quantity of 927%.

  19. Assessment of methane-related fuels for automotive fleet vehicles: technical, supply, and economic assessments

    Energy Technology Data Exchange (ETDEWEB)

    1982-02-01

    The use of methane-related fuels, derived from a variety of sources, in highway vehicles is assessed. Methane, as used here, includes natural gas (NG) as well as synthetic natural gas (SNG). Methanol is included because it can be produced from NG or the same resources as SNG, and because it is a liquid fuel at normal ambient conditions. Technological, operational, efficiency, petroleum displacement, supply, safety, and economic issues are analyzed. In principle, both NG and methanol allow more efficient engine operation than gasoline. In practice, engines are at present rarely optimized for NG and methanol. On the basis of energy expended from resource extraction to end use, only optimized LNG vehicles are more efficient than their gasoline counterparts. By 1985, up to 16% of total petroleum-based highway vehicle fuel could be displaced by large fleets with central NG fueling depots. Excluding diesel vehicles, which need technology advances to use NG, savings of 8% are projected. Methanol use by large fleets could displace up to 8% of petroleum-based highway vehicle fuel from spark-ignition vehicles and another 9% from diesel vehicles with technology advances. The US NG supply appears adequate to accommodate fleet use. Supply projections, future price differential versus gasoline, and user economics are uncertain. In many cases, attractive paybacks can occur. Compressed NG now costs on average about $0.65 less than gasoline, per energy-equivalent gallon. Methanol supply projections, future prices, and user economics are even more uncertain. Current and projected near-term methanol supplies are far from adequate to support fleet use. Methanol presently costs more than gasoline on an equal-energy basis, but is projected to cost less if produced from coal instead of NG or petroleum.

  20. A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst

    Science.gov (United States)

    Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

    2018-03-01

    The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

  1. Hydrogen-Permeable Tubular Membrane Reactor: Promoting Conversion and Product Selectivity for Non-Oxidative Activation of Methane over an Fe©SiO2Catalyst.

    Science.gov (United States)

    Sakbodin, Mann; Wu, Yiqing; Oh, Su Cheun; Wachsman, Eric D; Liu, Dongxia

    2016-12-23

    Non-oxidative methane conversion over Fe©SiO 2 catalyst was studied for the first time in a hydrogen (H 2 ) permeable tubular membrane reactor. The membrane reactor is composed of a mixed ionic-electronic SrCe 0.7 Zr 0.2 Eu 0.1 O 3-δ thin film (≈20 μm) supported on the outer surface of a one-end capped porous SrCe 0.8 Zr 0.2 O 3-δ tube. Significant improvement in CH 4 conversion was achieved upon H 2 removal from the membrane reactor compared to that in a fixed-bed reactor. The Fe©SiO 2 catalyst in the H 2 permeable membrane reactor demonstrated a stable ≈30 % C 2+ single-pass yield, with up to 30 % CH 4 conversion and 99 % selectivity to C 2 (ethylene and acetylene) and aromatic (benzene and naphthalene) products, at the tested conditions. The selectivity towards C 2 or aromatics was manipulated purposely by adding H 2 into or removing H 2 from the membrane reactor feed and permeate gas streams. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst

    KAUST Repository

    Aguilar Tapia, Antonio

    2018-03-22

    The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

  3. A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2catalyst.

    Science.gov (United States)

    Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

    2018-03-01

    The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO 2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

  4. Deactivation of Pd Catalysts by Water during Low Temperature Methane Oxidation Relevant to Natural Gas Vehicle Converters

    Directory of Open Access Journals (Sweden)

    Rahman Gholami

    2015-03-01

    Full Text Available Effects of H2O on the activity and deactivation of Pd catalysts used for the oxidation of unburned CH4 present in the exhaust gas of natural-gas vehicles (NGVs are reviewed. CH4 oxidation in a catalytic converter is limited by low exhaust gas temperatures (500–550 °C and low concentrations of CH4 (400–1500 ppmv that must be reacted in the presence of large quantities of H2O (10–15% and CO2 (15%, under transient exhaust gas flows, temperatures, and compositions. Although Pd catalysts have the highest known activity for CH4 oxidation, water-induced sintering and reaction inhibition by H2O deactivate these catalysts. Recent studies have shown the reversible inhibition by H2O adsorption causes a significant drop in catalyst activity at lower reaction temperatures (below 450 °C, but its effect decreases (water adsorption becomes more reversible with increasing reaction temperature. Thus above 500 °C H2O inhibition is negligible, while Pd sintering and occlusion by support species become more important. H2O inhibition is postulated to occur by either formation of relatively stable Pd(OH2 and/or partial blocking by OH groups of the O exchange between the support and Pd active sites thereby suppressing catalytic activity. Evidence from FTIR and isotopic labeling favors the latter route. Pd catalyst design, including incorporation of a second noble metal (Rh or Pt and supports high O mobility (e.g., CeO2 are known to improve catalyst activity and stability. Kinetic studies of CH4 oxidation at conditions relevant to natural gas vehicles have quantified the thermodynamics and kinetics of competitive H2O adsorption and Pd(OH2 formation, but none have addressed effects of H2O on O mobility.

  5. Critical influence of the amorphous silica-to-cristobalite phase transition on the performance of Mn/Na{sub 2}WO{sub 4}/SiO{sub 2} catalysts for the oxidative coupling of methane

    Energy Technology Data Exchange (ETDEWEB)

    Palermo, A. [UNMDP-CONICET, Mar del Plata (Argentina). Inst. of Materials Science and Technology; Vazquez, J.P.H. [CSIC-Univ. Sevilla-Junta de Andalucia (Spain). Inst. de Ciencia de Materiales; Lee, A.F.; Tikhov, M.S.; Lambert, R.M. [Univ. of Cambridge (United Kingdom). Dept. of Chemistry

    1998-07-25

    XRD, XPS/XAES, TPR analysis and catalytic testing have been applied to Na/W/Mn/SiO{sub 2} methane coupling catalysts and to corresponding formulations without one or more of Na, Mn, and W. The authors find a clear correlation between catalyst performance and support structure in the final calcined material. Amorphous silica yields active but very unselective catalysts. Crystalline SiO{sub 2} ({alpha}-cristobalite) generates active and highly selective catalysts--especially with respect to the formation of ethylene. The authors demonstrate that the presence of Na is essential for the anomalous low temperature silica {r_arrow} cristobalite support phase transition to occur. The structural, catalytic, and spectroscopic results indicate that Na plays a dual role as both structural and chemical promoter.

  6. Realization of a technical and economic referential of units of organic waste processing by methanization with and without biogas valorization. Study report

    International Nuclear Information System (INIS)

    2010-01-01

    Based on a literature survey and on the analysis of results obtained in operating installations in different countries (Germany, Denmark, France, Netherlands, and Switzerland), this study concerns the methanization of different substrates: domestic wastes, sludge from sewage processing plants, industrial wastes and effluents, agricultural wastes and effluents. This synthetic report describes the current status of methanization in terms of regulatory framework (for renewable energies, and for waste management, digestion residues and compost valorization in Europe and in the studied countries), and in terms of actual production and variety of base products. It gives an overview of the available technical solutions, of the products they use, and of the associated investment costs. These techniques are: completely stirred tank reactor (SCTR), upflow anaerobic sludge blanket (UASB), internal circulation (IC), 'piston', batch, percolation, contact, fluidized bed, and anaerobic filter. It reports a synthesis of answers given to a questionnaire about technical and economic aspects

  7. Computational Investigation of the Thermochemistry and Kinetics of Steam Methane Reforming Over a Multi-Faceted Nickel Catalyst

    KAUST Repository

    Blaylock, D. Wayne

    2011-08-20

    A microkinetic model of steam methane reforming over a multi-faceted nickel surface using planewave, periodic boundary condition density functional theory is presented. The multi-faceted model consists of a Ni(111) surface, a Ni(100) surface, and nickel step edge sites that are modeled as a Ni(211) surface. Flux and sensitivity analysis are combined to gain an increased understanding of the important reactions, intermediates, and surface facets in SMR. Statistical thermodynamics are applied to allow for the investigation of SMR under industrially-relevant conditions (e.g., temperatures in excess of 500 °C and pressures in excess of 1 bar). The most important surface reactions are found to occur at the under-coordinated step edge sites modeled using the Ni(211) surface as well as on the Ni(100) surface. The primary reforming pathway is predicted to be through C*+ O*→ CO*at high temperatures; however, hydrogen-mediated reactions such as C*+ OH*→ COH*and C.H.*+ O*→ CHO*are predicted to become more important at low temperatures. The rate-limiting reactions are predicted to be dissociative chemisorption of methane in addition to the aforementioned C-O addition reactions. © 2011 Springer Science+Business Media, LLC.

  8. Agricultural methanization

    International Nuclear Information System (INIS)

    2011-01-01

    After having briefly outlined the interest of the development of methanization of agricultural by-products in the context of struggle against climate change, and noticed that France is only now developing this sector as some other countries already did, this publication describes the methanization process also called anaerobic digestion, which produces a digestate and biogas. Advantages for the agriculture sector are outlined, as well as drawbacks and recommendations (required specific technical abilities, an attention to the use of energetic crops, an improved economic balance which still depends on public subsidies, competition in the field of waste processing). Actions undertaken by the ADEME are briefly evoked

  9. Tuning the composition of metastable CoxNiyMg100−xy(OH)(OCH3) nanoplates for optimizing robust methane dry reforming catalyst

    DEFF Research Database (Denmark)

    Fan, Xiaoli; Liu, Zhiting; Zhu, Yi-An

    2015-01-01

    Finding controllable, low-cost, and scalable ways to generate Ni-based catalysts is the bottleneck for methane dry reforming catalyst design. A new method for generating trimetallic CoxNiyMg100−x−yO solid solution platelets enclosed by (111) facets has been developed from the topotactic pyrolysis...

  10. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report, April--June 1992

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., AL (United States); Gutterman, C. [Foster Wheeler Development Corp., Livingston, NJ (United States); Chander, S. [Pennsylvania State Univ., University Park, PA (United States)

    1992-08-26

    Research in this project centers upon developing a new approach to the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates all aspects of the coal liquefaction process including coal selection, pretreatment, coal swelling with catalyst impregnation, coal liquefaction experimentation, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. The project is being carried out under contract to the United States Department of Energy. On May 28, 1992, the Department of Energy authorized starting the experimental aspects of this projects; therefore, experimentation at Amoco started late in this quarterly report period. Research contracts with Auburn University, Pennsylvania State University, and Foster Wheeler Development Corporation were signed during June, 1992, so their work was just getting underway. Their work will be summarized in future quarterly reports. A set of coal samples were sent to Hazen Research for beneficiation. The samples were received and have been analyzed. The literature search covering coal swelling has been up-dated, and preliminary coal swelling experiments were carried out. Further swelling experimentation is underway. An up-date of the literature on the liquefaction of coal using dispersed catalysts is nearing completion; it will be included in the next quarterly report.

  11. Novel catalysts for upgrading coal-derived liquids. Final technical progress report

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.T.; Savage, P.E.; Briggs, D.E.

    1995-03-31

    Research described in this report was aimed at synthesizing and evaluating supported Mo oxynitrides and oxycarbides for the selective removal of nitrogen, sulfur and oxygen from model and authentic coal-derived liquids. The Al{sub 2}O{sub 3}-supported oxynitrides and oxycarbides were synthesized via the temperature programmed reaction of supported molybdenum oxides or hydrogen bronzes with NH{sub 3} or an equimolar mixture of CH{sub 4} and H{sub 2}. Phase constituents and composition were determined by X-ray diffraction, CHN analysis, and neutron activation analysis. Oxygen chemisorption was used to probe the surface structure of the catalysts. The reaction rate data was collected using specially designed micro-batch reactors. The Al{sub 2}O{sub 3}-supported Mo oxynitrides and oxycarbides were competitively active for quinoline hydrodenitrogenation (HDN), benzothiophene hydrodesulfurization (HDS) and benzofuran hydrodeoxygenation (HDO). In fact, the HDN and HDO specific reaction rates for several of the oxynitrides and oxycarbides were higher than those of a commercial Ni-Mo/Al{sub 2}O{sub 3} hydrotreatment catalyst. Furthermore, the product distributions indicated that the oxynitrides and oxycarbides were more hydrogen efficient than the sulfide catalysts. For HDN and HDS the catalytic activity was a strong inverse function of the Mo loading. In contrast, the benzofuran hydrodeoxygenation (HDO) activities did not appear to be affected by the Mo loading but were affected by the heating rate employed during nitridation or carburization. This observation suggested that HDN and HDS occurred on the same active sites while HDO was catalyzed by a different type of site.

  12. Development and characterization of nickel catalysts supported in CeO2-ZrO2-Al2O3, CeO2-La2O3-Al2O3 e ZrO2-La2O3-Al2O3 matrixes evaluated for methane reforming reactions

    International Nuclear Information System (INIS)

    Abreu, Amanda Jordão de

    2012-01-01

    Nowadays, the methane reforming is large interest industrial for the take advantage of these gas in production the hydrogen and synthesis gas (syngas). Among in the reactions of methane stand of the reactions steam reforming and carbon dioxide reforming of methane. The main catalysts uses in the methane reforming is Ni/Al 2 O 3 . However, the supported-nickel catalyst is susceptible to the deactivation or the destruction by coke deposition. The carbon dissolves in the nickel crystallite and its diffuses through the nickel, leading for formation of the carbon whiskers, which results in fragmentation of the catalyst. Modification of such catalysts, like incorporation of suitable promoters, is desirable to achieve reduction of the methane hydrogenolysis and/or promotion of the carbon gasification. Catalysts 5%Ni/Al 2 O 3 supported on solid solutions formed by ZrO 2 -CeO 2 , La 2 O 3 and CeO 2 -ZrO 2 -La 2 O 3 were prepared, characterized and evaluated in reactions steam and carbon dioxide reforming and partial oxidation of methane with objective the value effect loading solution solid in support. The supports were prepared by co-precipitation method and catalysts were prepared by impregnation method and calcined at 500 deg C. The supports and catalysts were characterized by Nitrogen Adsorption, method -rays diffraction (XRD), X-rays dispersive spectroscopy (XDS), spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR) to and temperature programmed reduction (TPR), Raman Spectroscopy, X-ray absorption spectroscopy and Thermogravimetric Analysis. After all the catalytic reactions check which the addition of solid solution is beneficial for Ni/Al 2 O 3 catalysts and the best catalysts are Ni/CeO 2 -La 2 O 3 -Al 2 O 3 . (author)

  13. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    The title of my PhD thesis is “Design of Heterogeneous Catalysts”. Three reactions have been investigated: the methanation reaction, the Fischer-Tropsch reaction, and the NH3-based selective catalytic reduction (SCR) of NO. The experimental work performed in connection with the methanation reaction...... hydrogenation. For both systems a maximum in catalytic activity was found for some of the bimetallic catalysts being superior to the monometallic catalysts. This resulted in volcano curves for all investigated systems. In the Fischer-Tropsch reaction promotion of cobalt catalysts with manganese was studied...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

  14. Catalisadores Ni/Al2O3 promovidos com molibdênio para a reação de reforma a vapor de metano Mo-Ni/AL2O3 catalysts for the methane steam reforming reaction

    Directory of Open Access Journals (Sweden)

    Silvia Sálua Maluf

    2003-03-01

    Full Text Available Mo-promoted Ni/Al2O3 catalysts for the methane steam reforming reaction were studied in this work. The Ni/Al2O3 catalysts were prepared by precipitation and molibdenum was added by impregnation up to 2%wt. The solids were tested using a micro-reactor under two H2Ov/C conditions and were characterized by ICP-OES, XRD, N2 adsoption, H2 chemisorption and TPR. NiO and NiAl2O4 phases were observed and the metallic area decreased with the increase of the Mo content. From the catalytic tests high stability was verified for H2Ov/C=4.0. On the other hand, only the catalyst containing 0,05% Mo stayed stable during 30 hours of the test at H2Ov/C=2.0.

  15. Did state renewable portfolio standards induce technical change in methane mitigation in the U.S. landfill sector?

    Science.gov (United States)

    Delhotal, Katherine Casey

    Landfill gas (LFG) projects use the gas created from decomposing waste, which is approximately 49% methane, and substitute it for natural gas in engines, boilers, turbines, and other technologies to produce energy or heat. The projects are beneficial in terms of increased safety at the landfill, production of a cost-effective source of energy or heat, reduced odor, reduced air pollution emissions, and reduced greenhouse gas emissions. However, landfills sometimes face conflicting policy incentives. The theory of technical change shows that the diffusion of a technology or groups of technologies increases slowly in the beginning and then picks up speed as knowledge and better understanding of using the technology diffuses among potential users. Using duration analysis, data on energy prices, State and Federal policies related to landfill gas, renewable energy, and air pollution, as well as control data on landfill characteristics, I estimate the influence and direction of influence of renewable portfolio standards (RPS). The analysis found that RPS positively influences the diffusion of landfill gas technologies, encouraging landfills to consider electricity generation projects over direct sales of LFG to another facility. Energy price increases or increased revenues for a project are also critical. Barriers to diffusion include air emission permits in non-attainment areas and policies, such as net metering, which promote other renewables over LFG projects. Using the estimates from the diffusion equations, I analyze the potential influence of a Federal RPS as well as the potential interaction with a Federal, market based climate change policy, which will increase the revenue of a project through higher energy sale prices. My analysis shows that a market based climate change policy such as a cap-and-trade or carbon tax scheme would increase the number of landfill gas projects significantly more than a Federal RPS.

  16. Study of methanization resource and potential development in Aquitaine - Technical report. To keep on developing the methanization sector in the Dordogne district

    International Nuclear Information System (INIS)

    Priarollo, Jeremie; Michels, Julie; Jimenez, Julien

    2015-05-01

    This study aims at characterising territories of the Aquitaine region in terms of potential of development of individual, collective and territorial methanization units. The territory organic resource potential has first been assessed, and then combined with energetic outlets for biogas and outlets for digestates. A first phase aimed at providing a situational analysis of the methanization sector in the region. During a second phase, different resources of mobilisable organic wastes have been quantified, characterised and mapped at the district level in combination with energetic outlets (gas and heat) and digestate outlets. A third phase aimed at identifying and characterising areas of the different districts of the region displaying a methanization potential. After this report, a set of Power Point presentations is proposed which present this study under another form. Thus, these presentations contain graphs and data which illustrate these different aspects and issues: presentation of the different methanizable resources (quantitative results and maps), energy valorisation potential (co-generation and thermal outlets, injection into natural gas networks, definition and characterisation of areas displaying an interesting potential), presentation of a regional support arrangement (Methaqtion)

  17. Volume 1, 1st Edition, Multiscale Tailoring of Highly Active and Stable Nanocomposite Catalysts, Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Veser, Goetz

    2009-08-31

    Nanomaterials have gained much attention as catalysts since the discovery of exceptional CO oxidation activity of nanoscale gold by Haruta. However, many studies avoid testing nanomaterials at the high-temperatures relevant to reactions of interest for the production of clean energy (T > 700°C). The generally poor thermal stability of catalytically active noble metals has thus far prevented significant progress in this area. We have recently overcome the poor thermal stability of nanoparticles by synthesizing a platinum barium-hexaaluminate (Pt-BHA) nanocomposite which combines the high activity of noble metal nanoparticles with the thermal stability of hexaaluminates. This Pt-BHA nanocomposite demonstrates excellent activity, selectivity, and long-term stability in CPOM. Pt-BHA is anchored onto a variety of support structures in order to improve the accessibility, safety, and reactivity of the nanocatalyst. Silica felts prove to be particularly amenable to this supporting procedure, with the resulting supported nanocatalyst proving to be as active and stable for CPOM as its unsupported counterpart. Various pre-treatment conditions are evaluated to determine their effectiveness in removing residual surfactant from the active nanoscale platinum particles. The size of these particles is measured across a wide temperature range, and the resulting “plateau” of stability from 600-900°C can be linked to a particle caging effect due to the structure of the supporting ceramic framework. The nanocomposites are used to catalyze the combustion of a dilute methane stream, and the results indicate enhanced activity for both Pt-BHA as well as ceria-doped BHA, as well as an absence of internal mass transfer limitations at the conditions tested. In water-gas shift reaction, nanocomposite Pt-BHA shows stability during prolonged WGS reaction and no signs of deactivation during start-up/shut-down of the reactor. The chemical and thermal stability, low molecular weight, and

  18. Final Technical Report for GO15052 Intematix: Combinatorial Synthesis and High Throughput Screening of Effective Catalysts for Chemical Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Melman, Jonathan [Intematix Corporation, Fremont, CA (United States)

    2017-02-22

    The objectives of this project are: to discover cost-effective catalysts for release of hydrogen from chemical hydrogen storage systems; and to discover cost-effective catalysts for the regeneration of spent chemical hydrogen storage materials.

  19. Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States)

    2017-01-06

    An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources such as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.

  20. Catalysts and method

    Science.gov (United States)

    Taylor, Charles E.; Noceti, Richard P.

    1991-01-01

    An improved catlayst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HC1 and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  1. Methane Metabolism by Yeast

    Data.gov (United States)

    National Aeronautics and Space Administration — Our Technical Approach is to move the soluble Methane Monooxygenase system (sMMO) from methanotrophic bacteria into Pichi). sMMO consists of a hydroxylase (MMOH)...

  2. Rh promoted La0.75Sr0.25(Fe0.8Co0.2)1−xGaxO3-δ perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

    International Nuclear Information System (INIS)

    Palcheva, R.; Olsbye, U.; Palcut, M.; Rauwel, P.; Tyuliev, G.; Velinov, N.; Fjellvåg, H.H.

    2015-01-01

    Graphical abstract: - Highlights: • Perovskites type-oxide La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) prepared by the sol–gel citrate method. • Bulk and surface analysis to determine catalysts composition evolution. • Anaerobic catalytic partial oxidation of methane to syngas at 600 °C in a pulse apparatus over Rh promoted perovskites. • The catalysts showed high stability and selectivity. - Abstract: Synthesis gas production via selective oxidation of methane at 600 °C in a pulse reaction over La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) perovskite-supported rhodium catalysts, was investigated. The perovskite oxides were prepared by sol–gel citrate method and characterized by X-ray Diffraction (XRD), Moessbauer Spectroscopy (MS), Temperature Programmed Reduction (TPR-H 2 ), X-ray Photoelectron Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). According to XRD analysis, the synthesized samples were a single perovskite phase. The perovskite structure of Ga substituted samples remained stable after TPR-H 2 , as confirmed by XRD. Data of MS identified Fe 3+ ions in two distinctive coordination environments, and Fe 4+ ions. The Rh 2 O 3 thin overlayer was detected by the HRTEM for the Rh impregnated perovskite oxides. During the interaction of methane with oxidized perovskite-supported Rh (0.5 wt.%) catalysts, besides CO, H 2 , and surface carbon, CO 2 and H 2 O were formed. The Rh perovskite catalyst with x = 0.25 gallium exhibits the highest catalytic activity of 83% at 600 °C. The CO selectivity was affected by the reducibility of La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ perovskite materials.

  3. Technical note: Test of a low-cost and animal-friendly system for measuring methane emissions from dairy cows

    DEFF Research Database (Denmark)

    Hellwing, Anne Louise Frydendahl; Lund, Peter; Weisbjerg, Martin Riis

    2012-01-01

    Methane is a greenhouse gas with a significant anthropogenic contribution from cattle production. A demand exists for techniques that facilitate evaluation of mitigation strategies for dairy cows. Therefore, a low-cost system facilitating the highest possible animal welfare was constructed...

  4. Mechanistic insights into heterogeneous methane activation

    International Nuclear Information System (INIS)

    Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin; Yoo, Jong Suk; Kulkarni, Ambarish

    2017-01-01

    While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model to aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.

  5. Effect of Y{sub 2}O{sub 3} addition to Rh/Al{sub 2}O{sub 3} catalysts on the autothermal reforming of methane; Efeito da adicao de Y{sub 2}O{sub 3} a catalisadores de Rh/Al{sub 2}O{sub 3} na reforma autotermica do metano

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Vanessa Monteiro; Cardoso, Gabriel Alexandre Lima; Coutinho, Ana Carla da S. Lomba S.; Passos, Fabio Barboza [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e de Petroleo. Lab. de Reatores, Cinetica e Catalise (RECAT)]. E-mail: vanessafisqui@yahoo.com.br

    2008-07-01

    In this work, the effect of the addition of Y{sub 2}O{sub 3} (with 2%, 5% and 10% weight content) on Rh/{alpha}-Al{sub 2}O{sub 3} catalysts in the autothermal reforming reaction of methane to the production of hydrogen for fuel cells was investigated. The catalysts were characterized by the following techniques: N{sub 2} adsorption, H{sub 2} chemisorption, X-ray diffraction (XRD) and cyclohexane dehydrogenation reaction. The catalysts were also evaluated in the reaction of autothermal reforming. The catalyst with higher Y{sub 2}O{sub 3} content showed the best results both in the cyclohexane dehydrogenation rate and in the conversion of methane. (author)

  6. Fine particle clay catalysts for coal liquefaction. Quarterly technical progress report, May 9, 1992--August 8, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Olson, E.S.

    1995-10-01

    An investigation of new methods for the production of mixed pillared clay catalysts and clay-supported catalysts and determination of their catalytic activities were continued in this quarter. To demonstrate the reproducibility of the preparative method for high activity iron/alumina-pillared montmorillonite catalysts, a new batch of the catalyst was prepared and tested for hydrocracking activity with bibenzyl. This preparation gave conversion and product distribution similar to that reported previously. The mixed iron/alumina-pillared clay was also prepared using a pillaring solution that was aged for longer period of time. To determine the importance of the type of pillaring support in hydrocracking activity, iron/zirconia-pillared montmorillonite was prepared using the same technique as that for iron/alumina-pillared montmorillonite. The reaction of bibenzyl with the sulfided iron/zirconia-pillared catalyst gave a lower hydrocracking conversion than the iron/alumina-pillared catalyst. Addition of a second catalytic metal to the clay support was attempted to determine if a synergistic effect could improve liquefaction. Ferric nitrate and stannous chloride were added to the clay, but the resulting catalyst was relatively poor for hydrocracking and hydrogenation compared with ferric nitrate supported on the clay. New disposable iron catalysts with high acidity and surface area are desired for coal liquefaction. Synthetic iron aluminosilicates were prepared by methods similar to those used for the nickel-substituted synthetic mica montmorillonite (NiSMM) catalysts, which are very effective for hydrogenation and reforming of hydrocarbons. The iron aluminosilicate catalysts were tested for hydrocracking and hydrogenation of bibenzyl, naphthalene and pyrene. Pyrene hydrogenation was effectively catalyzed by the sulfided synthetic iron catalyst.

  7. Investigation of syngas interaction in alcohol synthesis catalysts. Quartery technical progress report, July 1, 1995--September 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Akundi, M.A.

    1996-02-01

    This report presents the work done on {open_quotes}Investigation of Syngas Interaction in Alcohol Synthesis Catalysts{close_quotes} during the last three months. In this report the results of the work done on the effect of CO adsorption on the magnetic character of cobalt in the Cu/Co/Cr catalysts is discussed.

  8. Preparation of a Ni-MgO-Al2O3 catalyst with high activity and resistance to potassium poisoning during direct internal reforming of methane in molten carbonate fuel cells

    Science.gov (United States)

    Jang, Won-Jun; Jung, You-Shick; Shim, Jae-Oh; Roh, Hyun-Seog; Yoon, Wang Lai

    2018-02-01

    Steam reforming of methane (SRM) is conducted using a series of Ni-MgO-Al2O3 catalysts for direct internal reforming (DIR) in molten carbonate fuel cells (MCFCs). Ni-MgO-Al2O3 catalysts are prepared by the homogeneous precipitation method with a variety of MgO loading amounts ranging from 3 to 15 wt%. In addition, each precursor concentrations are systemically changed (Ni: 1.2-4.8 mol L-1; Mg: 0.3-1.2 mol L-1; Al: 0.4-1.6 mol L-1) at the optimized composition (10 wt% MgO). The effects of MgO loading and precursor concentration on the catalytic performance and resistance against poisoning of the catalyst by potassium (K) are investigated. The Ni-MgO-Al2O3 catalyst with 10 wt% MgO and the original precursor concentration (Ni: 1.2 mol L-1; Mg: 0.3 mol L-1; Al: 0.4 mol L-1) exhibits the highest CH4 conversion and resistance against K poisoning even at the extremely high gas space velocity (GHSV) of 1,512,000 h-1. Excellent SRM performance of the Ni-MgO-Al2O3 catalyst is attributed to strong metal (Ni) to alumina support interaction (SMSI) when magnesium oxide (MgO) is co-precipitated with the Ni-Al2O3. The enhanced interaction of the Ni with MgO-Al2O3 support is found to protect the active Ni species against K poisoning.

  9. A Study of Deactivating Carbon Species during Methanation on a Ni/Al2O3 Catalyst

    DEFF Research Database (Denmark)

    Olesen, Sine Ellemann

     natural gas and as the infrastructure is already in place for natural gas, it is an attractive alternative to depleting oil resources. Catalysts based on nickel are the most common choice within industry due to the relatively low price of nickel and its acceptable performance. However, nickel catalysts...

  10. Autothermal reforming of methane in Pt/ZrO{sub 2}/Al{sub 2}O{sub 3} catalysts for hydrogen generation; Reforma autotermica do metano em catalisadores de Pt/ZrO{sub 2}/Al{sub 2}O{sub 3} para geracao de hidrogenio

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Mariana de Mattos Vieira Mello; Schmal, Martin [Coordenacao dos Programas de Pos-graduacao de Engenharia (COPPE/UFRJ), Rio de Janeiro, RJ (Brazil). Programa de Engenharia Quimica. Nucleo de Catalise

    2004-07-01

    Autothermal reforming of methane, combining steam reforming and partial oxidation was carried out with Pt/Al{sub 2}O{sub 3}, Pt/ZrO{sub 2} and Pt/ZrO{sub 2}/Al{sub 2}O{sub 3} catalysts, in the temperature range of 400-900 deg C. The Pt/ZrO{sub 2}/Al{sub 2}O{sub 3} catalyst was found to be the most active and stable at 800 deg C due to the higher resistance to coke formation. The reaction occurs in two simultaneous stages: total combustion of methane and reforming of the unconverted methane with steam and CO{sub 2}, with the O{sub 2} conversion of 100% starting from 450 deg C. The addition of O{sub 2} to the feed increases methane conversion and the catalyst stability, decreasing the H{sub 2} and CO yields due to the enhancement of methane combustion. By manipulating the O{sub 2}/CH{sub 4} ratio to the feed it is possible to achieve higher H{sub 2}/CO ratio and thus maximize hydrogen yield. (author)

  11. Role of CeO2 promoter in NiO/α-Al2O3 catalyst for dry reforming of methane

    Science.gov (United States)

    Loc, Luu Cam; Phuong, Phan Hong; Tri, Nguyen

    2017-09-01

    A series of Ni/α-Al2O3 (NiAl) catalysts promoted by CeO2 was prepared by co-impregnation methods with content of (NiO+CeO2) being in the range of 10-30 wt%. The NiO:CeO2 weight ratio was fluctuated at 1:1, 1:2 and 1:3. Several techniques, including X-ray powder diffraction (XRD), Hydrogen temperature-programmed reduction (H2-TPR), and transmission electron microscopy (TEM) were used to investigate catalysts' physico-chemical properties. The activity of these catalysts in dry reforming of CH4 was investigated at temperature range of 550-800 °C. The results revealed that the most suitable CeO2 promoted Ni catalyst contained 20 wt% of (NiO+CeO2) and NiO:CeO2 weight ratio of 1:2. The best catalytic performance of catalyst [20(1Ni2Ce)Al] due to a better reducibility resulted in a higher amount of free small particle NiO. At 700 °C and CH4:CO2 molar ratio of 1:1, the conversion of CH4 and CO2 on the most suitable CeO2 promoted Ni catalyst reached 86% and 67%, respectively; H2 and CO selectivity of 90% and H2:CO molar ratio of 1.15 were obtained. Being similar to MgO [1], promoter CeO2 could improve catalytic activity of Ni/α-Al2O3 catalyst at a lower range of temperature. Besides, both MgO and CeO2 had a great impact on improving coke resistance of Ni catalysts. At higher temperature, the role of CeO2 as well as MgO in preventing coke formation on catalyst was clarified by temperature-programmed oxidation (TPO) technique. Coke amount formed after 30-h TOS on 20(1Ni2Ce) catalyst was found to be 22.18 mgC/gcat, being less than on non-promoted catalyst (36.75 mgC/gcat), but more than on 20(1Ni2Mg)Al one (5.25 mgC/gcat).

  12. Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

    Directory of Open Access Journals (Sweden)

    Anna M. Venezia

    2013-06-01

    Full Text Available Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-07-01

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

  14. Structural changes of noble metal catalysts during ignition and extinction of the partial oxidation of methane studied by advanced QEXAFS techniques

    DEFF Research Database (Denmark)

    Grunwaldt, Jan-Dierk; Beier, M.; Kimmerle, B.

    2009-01-01

    The dynamics of the ignition and extinction of the catalytic partial oxidation (CPO) of methane to hydrogen and carbon monoxide over Pt-Rh/Al2O3 and Pt/Al2O3 were studied in the subsecond timescale using quick-EXAFS with a novel cam-driven X-ray monochromator employing Si(111) and Si(311) crystal...... of the CPO of methane and are complementing results from time-resolved infrared thermography and full field X-ray microscopy studies....

  15. Technical note: In vitro total gas and methane production measurements from closed or vented rumen batch culture systems.

    Science.gov (United States)

    Cattani, M; Tagliapietra, F; Maccarana, L; Hansen, H H; Bailoni, L; Schiavon, S

    2014-03-01

    This study compared measured gas production (GP) and computed CH4 production values provided by closed or vented bottles connected to gas collection bags. Two forages and 3 concentrates were incubated. Two incubations were conducted, where the 5 feeds were tested in 3 replicates in closed or vented bottles, plus 4 blanks, for a total of 64 bottles. Half of the bottles were not vented, and the others were vented at a fixed pressure (6.8 kPa) and gas was collected into one gas collection bag connected to each bottle. Each bottle (317 mL) was filled with 0.4000 ± 0.0010 g of feed sample and 60 mL of buffered rumen fluid (headspace volume = 257 mL) and incubated at 39.0°C for 24 h. At 24 h, gas samples were collected from the headspace of closed bottles or from headspace and bags of vented bottles and analyzed for CH4 concentration. Volumes of GP at 24 h were corrected for the gas dissolved in the fermentation fluid, according to Henry's law of gas solubility. Methane concentration (mL/100mL of GP) was measured and CH4 production (mL/g of incubated DM) was computed using corrected or uncorrected GP values. Data were analyzed for the effect of venting technique (T), feed (F), interaction between venting technique and feed (T × F), and incubation run as a random factor. Closed bottles provided lower uncorrected GP (-18%) compared with vented bottles, especially for concentrates. Correction for dissolved gas reduced but did not remove differences between techniques, and closed bottles (+25 mL of gas/g of incubated DM) had a greater magnitude of variation than did vented bottles (+1 mL of gas/g of incubated DM). Feeds differed in uncorrected and corrected GP, but the ranking was the same for the 2 techniques. The T × F interaction influenced uncorrected GP values, but this effect disappeared after correction. Closed bottles provided uncorrected CH4 concentrations 23% greater than that of vented bottles. Correction reduced but did not remove this difference. Methane

  16. Toward highly efficient in situ dry reforming of H2S contaminated methane in solid oxide fuel cells via incorporating a coke/sulfur resistant bimetallic catalyst layer

    NARCIS (Netherlands)

    Hua, B.; Yan, N.; Li, M.; Sun, Y.-F.; Chen, J.; Zhang, Y.-Q.; Li, J.; Etsell, T.; Sarkar, P.; Luo, J.L.

    2016-01-01

    The escalating global warming effects are a reason for immediate measures to reduce the level of greenhouse gases. In this context, dry reforming of methane (DRM), an old yet both scientifically and industrially important process, is making a comeback in contributing to the utilization of CO2.

  17. Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Final technical report, October 1990--December 1994

    Energy Technology Data Exchange (ETDEWEB)

    Osseo-Asare, K.; Boakye, E.; Vittal, M. [and others

    1995-04-01

    This report described the synthesis of Molybdenum Sulfides in microemulsions by acidification of ammonium tetrathiomolybdate. Molybdenum Sulfides have been shown to be potential coal liquefaction catalysts. The importance of particle size, temperature effects, and coal surface chemistry to impregnation are discussed.

  18. Superior catalysts for selective catalytic reduction of nitric oxide. Annual technical report, September 30, 1993--September 29, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Chen, J.P.; Hausladen, M.C.; Yang, R.T.

    1995-03-01

    A delaminated Fe{sub 2}O{sub 3}-pillared clay catalyst was prepared for the selective catalytic reduction (SCR) of NO by NH{sub 3} at above 300{degrees}C. The delaminated pillard clay was characterized by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectroscopy) chemical analysis, XRD (X-ray diffraction) structure and line broadening analyses, micropore size probing, and Moessbauer analysis. These analyses showed that the catalyst contained fragmented Fe{sub 2}O{sub 3}-pillared clay forming {open_quotes}house-of-cards{close_quotes} structure with dispersed Fe{sub 2}O{sub 3} particles approximately 170 {angstrom} in size. The SCR activity of the delaminated pillard clay was higher than the commercial-type V{sub 2}O{sub 5} + WO{sub 3}/TiO{sub 2} catalyst, and also higher than the undelaminated pillard clay and supported Fe{sub 2}O{sub 3} catalysts, under conditions with SO{sub 2}. Infrared measurements of adsorbed NH{sub 3} showed strong Bronsted acidity which was caused possibly by interactions between Fe{sub 2}O{sub 3} and clay.

  19. Catalysts and process developments for two-stage liquefaction. Final technical report, October 1, 1989--September 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Cronauer, D.C.; Swanson, A.J.; Sajkowski, D.J.

    1992-12-31

    Research in this project centered upon developing and evaluating catalysts and process improvements for coal liquefaction in the two-stage, close-coupled catalytic process. The major results are summarized here and they are described in more detail under each Task. In tasks for coal pretreatment and beneficiation, it was shown for coal handling that drying of both lignite or subbituminous coals using warm air, vacuum oven or exposing to air for long time was detrimental to subsequent liquefaction. Both laboratory and bench-scale beneficiations indicated that in order to achieve increased liquefaction yield for Illinois No. 6 bituminous coal, size separation with in sink-float technique should be used. For subbituminous coal, the best beneficiation was aqueous SO{sub 2} treatment, which reduced mineral matter. In the case of lignite, the fines should be rejected prior to aqueous SO{sub 2} treatment and sink-float gravity separation. In liquefying coals with supported catalysts in both first and second stages, coal conversion was highest (93%) with Illinois No. 6 coal, which also had the highest total liquid yield of 80%, however, the product contained unacceptably high level of resid (30%). Both low rank coals gave lower conversion (85--87%) and liquid yields (57--59%), but lighter products (no resid). The analysis of spent first stage catalysts indicated significant sodium and calcium deposits causing severe deactivation. The second stage catalysts were in better condition showing high surface areas and low coke and metal deposits. The use of dispersed catalyst in the first stage would combat the severe deactivation.

  20. Production of hydrogen with methane decomposition using Ni-Mn/Ce-ZrO{sub 2} catalysts; Produccion de hidrogeno via descomposicion de metano mediante catalizadores de Ni-Mn/Ce-ZrO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, C.; Hernandez-Pichardo, M.L.; Valenzuela, M. A. [Instituto Politecnico Nacional-ESIQIE, Mexico, D.F. (Mexico)]. E-mail: mhernandezp@ipn.mx; Del Angel, P.; Montoya de la Fuente, J.A. [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico)

    2009-09-15

    The catalytic decomposition of methane makes it possible to obtain CO and CO{sub 2} free hydrogen, which is a desirable characteristic for fuel cell applications. In addition, this method simultaneously obtains diverse carbon nanostructures with a large variety of applications. This work prepared catalysts with different Ni contents supported by Ce-Zr mixed oxides and doped with manganese to promote activity. The supports were synthesized with surfactant-assisted coprecipitation. The Ni and Mn deposits were performed using conventional impregnation for evaluation in the methane decomposition catalyst at 500 degrees Celsius. It was observed that with the incorporation of 1% of Mn into the Ni0 active phase, the conversion of methane into hydrogen and carbon nanostructures increased. The results of reduction at the programmed temperature indicate that the addition of Mn enables the formation of different NiO{sub x} species, increasing dispersion and the degree of reduction to Ni0. Analyses with electron and transmission microscopy show the formation of distinct species of carbon, including nanotubes, nanofibers and concentric onion-like structures, as well as a significant formation of encapsulated Ni0 particles. [Spanish] La descomposicion catalitica de metano permite la obtencion de hidrogeno libre de CO y CO{sub 2}, lo cual es una caracteristica deseable para su aplicacion en celdas de combustible. Ademas, por esta ruta, simultaneamente se obtienen diversas nanoestructuras de carbono con una gran variedad de aplicaciones. En este trabajo se prepararon catalizadores con diferentes contenidos de Ni soportados en oxidos mixtos Ce-Zr y se doparon con manganeso como promotor de actividad. Los soportes se sintetizaron por coprecipitacion asistida por surfactante y el deposito del Ni y del Mn se efectuo por impregnacion convencional para su evaluacion en la descomposicion catalitica de metano a 500 grados centigrados. Se observo que mediante la incorporacion de 1% de Mn a

  1. Combinatorial and conventional studies on new highly selective methanation catalysts for the removal of small amounts of CO from hydrogen-rich gas mixtures; Kombinatorische und konventionelle Untersuchungen zu neuen hochselektiven Methanisierungskatalysatoren zur Entfernung geringer Mengen an CO aus wasserstoffreichen Gasgemischen

    Energy Technology Data Exchange (ETDEWEB)

    Kraemer, Michael

    2008-04-15

    New tailor-made catalysts for the purification of hydrogen-rich reformates by the selective methanation of CO were developed using combinatorial methods. The optimization of the catalysts was achieved within 3 or 4 generations while Ni-based oxides generally proved most promising. Conventional validations confirmed the successive enhancement of the materials. All in all, a number of catalysts providing higher CO hydrogenation activities combined with a lower reactivity towards the undesired methanation of the excess CO{sub 2} in comparison to an industrial reference was discovered. The application of numerous characterization techniques to the optimization sequence Ni{sub 100} - Zr{sub 10}Ni{sub 90} - Re{sub 2}Zr{sub 10}Ni{sub 88} - Re{sub 0,6}Zr{sub 15}Ni{sub 84,4} resulted in the following model: The catalysts are present in their as-prepared state as mixed metal oxide, which is (partly) demixed during the reductive pretreatment. The resulting (Re)Ni-particles seem to represent the actual active component while ZrO{sub 2} could stabilize the dispersion. Alloying with Ni, Re seems to modify the surface of the catalyst in such a way that it only marginally interacts with CO{sub 2}. Solo methanation tests unambiguously reveal that the increase in selectivity is not connected to a competition between CO and CO{sub 2} for adsorption sites but is based on a loss of the intrinsic reactivity of the respective samples towards the methanation of CO{sub 2}. (orig.)

  2. Investigation of activity and selectivity of redox catalysts in oxidative ...

    African Journals Online (AJOL)

    In this study, oxidative coupling of methane on Redox catalysts in fluidized bed reactor was investigated. For this purpose, the catalyst Mn-Na2WO4/SiO2 was selected as a Redox catalyst. In order to investigate this catalyst, transient state experiments were designed and performed. Then, the different reaction conditions on ...

  3. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report, July--September 1992

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., AL (United States); Gutterman, C. [Foster Wheeler Development Corp., Livingston, NJ (United States); Chander, S. [Pennsylvania State Univ., University Park, PA (United States)

    1992-12-31

    The experimental study of coal swelling ratios have been determined with a wide variety of solvents. Only marginal levels of coal swelling were observed for the hydrocarbon solvents, but high levels were found with solvents having heteroatom functionality. Blends were superior to pure solvents. The activity of various catalyst precursors for pyrene hydrogenation and coal conversion was measured. Higher coal conversions were observed for the S0{sub 2}-treated coal than the raw coal, regardless of catalyst type. Coal conversions were highest for Molyvan-L, molybdenum naphthenate, and nickel octoate, respectively. Bottoms processing consists of a combination of the ASCOT process coupling solvent deasphalting with delayed coking. Initial results indicate that a blend of butane and pentane used near the critical temperature of butane is the best solvent blend for producing a yield/temperature relationship of proper sensitivity and yet retaining an asphalt phase of reasonable viscosity. The literature concerning coal swelling, both alone and in combination with coal liquefaction, and the use of dispersed or unsupported catalysts in coal liquefaction has been updated.

  4. Configurational diffusion of asphaltenes in fresh and aged catalyst extrudates. Final technical report, September 20, 1991--September 30, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Guin, J.A.

    1998-12-31

    The overall objective of this project was to investigate the diffusion of coal and petroleum asphaltenes in the pores of a supported catalyst. Experimental measurements together with mathematical modeling was conducted to determine how the diffusion rate of asphaltenes, as well as some model compounds, depended on molecule sizes and shapes. The process of diffusion in the pores of a porous medium may occur by several mechanisms. Hindered diffusion occurs when the sizes of the diffusion molecules are comparable to those of the porous pores through which they are diffusing. Hindered diffusion phenomena have been widely observed in catalytic hydrotreatment of asphaltenes, heavy oils, coal derived liquids, etc. Pore diffusion limitations can be greater in spent catalysts due to the deposition of coke and metals in the pores. In this work, a general mathematical model was developed for the hindered diffusion-adsorption of solute in a solvent onto porous materials, e. g. catalysts, from a surrounding bath. This diffusion model incorporated the nonuniformities of pore structures in the porous media. A numerical method called the Method of Lines was used to solve the nonlinear partial differential equations resulting from the mathematical model. The accuracy of the numerical solution was verified by both a mass balance in the diffusion system and satisfactory agreement with known solutions in several special cases.

  5. Study of the microstructure of the tetragonal phase of the ZrO2 for its use like support of active catalysts for the dry reforming reaction of methane

    International Nuclear Information System (INIS)

    Mosimann, C. B; Cornaglia, L. M

    2005-01-01

    Zirconium oxide is widely employed as support in catalysts for methane reforming with carbon dioxide. Zirconia can be found in three crystalline phases: monoclinic ZrO 2 (m), tetragonal ZrO 2 (t), and cubic.Studies of zirconia crystallization in the ZrO 2 -SiO 2 sol-gel system have reported that the tetragonal phase was the first phase to crystallize, between 300 and 500 degrees C, and that the transformation from tetragonal to monoclinic zirconia occurs at 1000 degrees C, being observed in rich compositions only (> 80%).The application of new methods of preparation and the use of dopants such as La, Si or sulfate has lately allowed the obtention of zirconia with high surface areas, even after calcination at 700 degrees C.The aqueous method which produces zirconium hydroxide as intermediate, followed by calcination, is one of the most widely used methods due to its great flexibility to allow the preparation of doped zirconia.On the other hand, La 2 O 3 used as support in methane dry reforming is known for its capacity to form lanthanum oxi carbonate phases which would participate in the catalytic cycle, providing active sites which react with the deposited carbon.The aim of this work was twofold: study the effect of the lanthanum doping performed by impregnation of zirconium hydroxide upon the stability of the tetragonal phase, and develop an active catalyst for the methane dry reforming reaction.Zr(OH) 4 (Mel Chemicals) was employed performing different thermal treatments: calcination at 400 and 510 degrees C for 8 hs; at 550, 600 and 800 degrees C for 12 hs, and at 1100 degrees C for 15 hs.The preparation of the ZrO 2 support doped with La was performed by means of the humid impregnation method, starting from Zr(OH) 4 and the La(NO 3 ) 3 .6H 2 O salt (Anedra).The concentration was 5 and 8% in weight of La 2 O 3 .The solids obtained were calcined at 400 and 600 degrees C.The Rh(0.6%)/La 2 O 3 (5%)-ZrO 2 was prepared by the same method.A solution of the RhCl 3 .3H

  6. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification.

    Science.gov (United States)

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G; Kazantzis, Nikolaos K; Ma, Yi Hua

    2016-09-19

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H₂ to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H₂, CO and CO₂. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H₂O, CO₂ and H₂. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H₂ and induce higher methane and CO conversions while yielding ultrapure H₂ and compressed CO₂ ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H₂ permeance and purity, high CH₄ conversion levels and reduced CO yields.

  7. The impact of copper in LaNi{sub 1-x}Cu{sub x}O{sub 3} perovskite-like structures used as catalyst precursors for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Vlach, K.; Hoang, D.L.; Armbruster, U.; Martin, A. [Leibniz-Institut fuer Katalyse e.V. an der Universitaet Rostock (Germany)

    2013-11-01

    This work deals with the synthesis of perovskite-like catalyst precursors (LaNi{sub 1-x}Cu{sub x}O{sub 3} with x = 0, 0.2, 0.5, 0.8, 1). These precursors were used to catalyse the dry reforming of methane (DRM) reaction carried out at 973 K, CH{sub 4}/CO{sub 2} = 1 and a GHSV = 18,000 ml/g/h. The precursors were transformed during the course of the reaction to give Ni-Cu/La{sub 2}O{sub 3} solids. We found out that the activity increases with raising Ni content but small Cu admixture suppresses the coke formation substantially. XRD and TEM measurements showed that the transformation led to the formation of small metallic Ni and/or Cu particles. In addition also alloying can be observed. The best catalytic system with respect to activity and suppressed carbon deposition was Ni{sub 0.8}-Cu{sub 0.2}/La{sub 2}O{sub 3} (X{sub CH4} = 61%, X{sub CO2} = 67%). (orig.)

  8. Estudo microestrutural do catalisador Ni/gama-Al2O3: efeito da adição de CeO2 na reforma do metano com dióxido de carbono Microstructural study of Ni/gamma-Al2O3 catalyst: addition effects of CeO2 on carbon dioxide reforming of methane

    Directory of Open Access Journals (Sweden)

    Antoninho Valentini

    2003-10-01

    Full Text Available The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the gamma-Al2O3/CeO2 system prepared by wet impregnation. With the increase of the CeO2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO2 was observed to the Ni/CeO2 sample after activation in a H2 atmosphere above 300 ºC. Such behavior has a significantly influence on the catalytic activity.

  9. A combustão catalítica do metano: estudo estatístico do efeito das variáveis de preparação e pré-tratamento de catalisadores de paládio suportado sobre a atividade catalítica The catalytic combustion of methane: statistical study of preparation and pretreatment conditions of palladium supported catalysts and their relationship with catalytic activity

    Directory of Open Access Journals (Sweden)

    Maria da Graça Carneiro da Rocha

    2001-04-01

    Full Text Available The catalytic combustion of methane on alumina supported palladium catalysts was studied. It has been reported that the activity of the catalyst increases with its time on line, despite of an increase of the palladium particle size. However, different preparation, pretreatment and testing conditions can be the reason for the observed different results. An experimental design, which allows to verify the influence of several parameters at the same time with a good statistical quality, was used. A Plackett-Burman design was selected for the screening of the variables which have an effect on the increase of the catalyst activity.

  10. Accelerating process and catalyst development in reforming reactions with high throughput technologies under industrially relevant conditions

    Energy Technology Data Exchange (ETDEWEB)

    Schunk, S.A.; Bollmann, G.; Froescher, A.; Kaiser, H.; Lange de Oliveira, A.; Roussiere, T.; Wasserschaff, G. [hte Aktiengesellschaft, Heidelberg (Germany); Domke, I. [BASF SE, Ludwigshafen (Germany)

    2010-12-30

    The generation of hydrogen via reforming of a variety of carbon containing feed-stocks in the presence of water is up to date one of the most versatile technologies for the production of hydrogen and syngas. Although these reforming technologies are in principle well established, understood and commercialized, there are still a number of technological challenges that are not solved up to a satisfactorily degree and there is a constant demand for appropriate answers to the challenges posed. High throughput experimentation can be a valuable tool in helping accelerate the development of suitable solutions on the catalyst and process development side. In order to be able to generate test data that are close or identical to process relevant conditions, hte has developed a new technology portfolio of test technologies named Stage-IV technology. In contrast to earlier developments which address more small scale testing on the basis of catalyst volumes of 1ml up to 10 ml under isothermal conditions, our new technology portfolio offers the advantage of test volumes at sub-pilot scale also realizing reactor dimensions close to technical applications. This does not only ensure a good mimic of the hydrodynamic conditions of the technical scale, but also allows a fingerprinting of features like temperature gradients in the catalyst bed which play a large role for catalyst performance. Apart from catalyst tests with granulates when screening for optimized catalyst compositions, the units are designed to accommodate tests with shaped catalysts. In order to demonstrate how these technologies can accelerate catalyst and process development we have chosen technically challenging application examples: (I) Pre-reforming and reforming of methane based feeds which accelerate coking and catalyst deactivation. Higher reaction pressures, high CO{sub 2} contents in the feedgas (which occur typically in sources like bio-gas or certain types of natural gas), the presence of higher alkanes

  11. Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy

    DEFF Research Database (Denmark)

    Grunwaldt, Jan-Dierk; Kimmerle, B.; Baiker, A.

    2009-01-01

    Spectroscopic studies on heterogeneous catalysts have mostly been done in an integral mode. However, in many cases spatial variations in catalyst structure can occur, e.g. during impregnation of pre-shaped particles, during reaction in a catalytic reactor, or in microstructured reactors...... to efficiently determine the distribution of the oxidation state of a catalyst inside a reactor under reaction conditions. The new technical approaches together with quantitative data analysis and an appropriate in situ catalytic experiment allowed drawing important conclusions on the reaction mechanism......, and the analytical strategy might be similarly applied in other case studies. The corresponding temperature profiles and the catalytic performance were measured by means of an IR-camera and mass spectrometric analysis. In a more advanced experiment the ignition process of the partial oxidation of methane...

  12. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October 1995--December 1995

    Energy Technology Data Exchange (ETDEWEB)

    Song, C.; Cooke, W.S.; Schmidt, E.; Schobert, H.H.

    1996-02-01

    Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting polycyclic aromatic units and the reactions of various oxygen functional groups. Here in this quarterly, we report on the catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds in the reactions of dibenzothiophene (DBT) with hydrogen under conditions related to coal liquefaction. The catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds have been examined in the hydrogenation and hydrodesulfurization reactions of dibenzothiophene (DBT) under conditions related to coal liquefaction. The metal compounds are candidate catalyst precursors for direct coal liquefaction. The reactions were carried out in batch microautoclave reactors at 400{degrees}C for 30 minutes with 6.9 MPa (cold) hydrogen pressure, and tridecane solvent. A metal loading of 0.5 mol% resulted in low conversion and only hydrogenation. Addition of sulfur in 4:1 molar ratio led only to a minor increase in conversion and hydrodesulfurization. The use of a higher boiling solvent (octadecane vs. tridecane) was beneficial in providing increased conversion, hydrodesulfurization, and hydrogenation. An increase in metal compound loading to 36.2 mol% led to a dramatic increase in conversion, hydrodesulfurization, and hydrocracking. Molybdenum hexacarbonyl at 36 mol% loading, with added sulfur at 6:1 ratio and octadecane solvent, gave 100% conversion of dibenzothiophene to other products with 100% hydrodesulfurization. Ammonium tetrathiomolybdate and molybdenum(III) chloride are less active under similar conditions. A cobalt-molybdenum thiocubane complex gave unexpectedly low conversions. Iron and cobalt carbonyls also provided very low conversions, even with added sulfur.

  13. La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO 2 reforming of methane

    Science.gov (United States)

    Valderrama, Gustavo; Kiennemann, Alain; Goldwasser, Mireya R.

    La 1- xSr xNi 0.4Co 0.6O 3 and La 0.8Sr 0.2Ni 1- yCo yO 3 solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO 2 to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH 4/CO 2 = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La 0.9Sr 0.1CoO 3 and/or La 0.9Sr 0.1NiO 3 as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni 0, Co 0 with particle sizes in the range of nanometers over the SrO and La 2O 3 phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction.

  14. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

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

  15. Catalyst study for the plasma exhaust purification process

    International Nuclear Information System (INIS)

    Chabot, J.; Sannier, J.

    1990-01-01

    Several catalysts available from commercial sources have been screened to find out specific catalysts which allow complete methane oxidation and ammonia decomposition at temperature as low as possible in order to minimize tritium loss by permeation through processing equipment walls. Afterwards, an extended kinetic investigation has been performed on the best catalysts to achieve the data necessary to unit calculations. For methane oxidation, a palladium on alumina catalyst shows a very satisfactory low-temperature efficiency while a non-precious metal catalyst made of nickel oxide and alumina was found to be the more efficient for ammonia decomposition

  16. Arctic methane

    NARCIS (Netherlands)

    Dyupina, E.; Amstel, van A.R.

    2013-01-01

    What are the risks of a runaway greenhouse effect from methane release from hydrates in the Arctic? In January 2013, a dramatic increase of methane concentration up to 2000 ppb has been measured over the Arctic north of Norway in the Barents Sea. The global average being 1750 ppb. It has been

  17. Keys to methane conversion technologies

    Energy Technology Data Exchange (ETDEWEB)

    Lange, J.P.; De Jong, K.P. [Shell Research, Koninklijke/Shell-Laboratorium, Amsterdam (Netherlands); Ansorge, J. [Shell Internationale Petroleum Maatschappij, The Hague (Netherlands); Tijm, P.J.A. [Shell International Gas Ltd, Shell Center, London (United Kingdom)

    1997-12-31

    Numerous process schemes have been put forward for converting methane to liquid hydrocarbon fuels. A proper selection and design of new or emerging methane conversion processes requires insight into the technical and economic issues that are critical for their viability. Three process requirements will be highlighted here, namely large plant scale, high thermal efficiency and low overall heat and momentum transfer duty. Since the overall heat and momentum transfer duty is strongly affected by the achievable yield per pass, the parameters which seem to rule the maximum yield per pass of methane conversion routes are also investigated. 15 refs.

  18. Producing Hydrogen by Plasma Pyrolysis of Methane

    Science.gov (United States)

    Atwater, James; Akse, James; Wheeler, Richard

    2010-01-01

    Plasma pyrolysis of methane has been investigated for utility as a process for producing hydrogen. This process was conceived as a means of recovering hydrogen from methane produced as a byproduct of operation of a life-support system aboard a spacecraft. On Earth, this process, when fully developed, could be a means of producing hydrogen (for use as a fuel) from methane in natural gas. The most closely related prior competing process - catalytic pyrolysis of methane - has several disadvantages: a) The reactor used in the process is highly susceptible to fouling and deactivation of the catalyst by carbon deposits, necessitating frequent regeneration or replacement of the catalyst. b) The reactor is highly susceptible to plugging by deposition of carbon within fixed beds, with consequent channeling of flow, high pressure drops, and severe limitations on mass transfer, all contributing to reductions in reactor efficiency. c) Reaction rates are intrinsically low. d) The energy demand of the process is high.

  19. Breaking methane

    OpenAIRE

    Rosenzweig, Amy C.

    2015-01-01

    The most powerful oxidant found in nature is compound Q, an enzymatic intermediate that oxidizes methane. New spectroscopic data have resolved the long-running controversy about Q’s chemical structure.

  20. The Methanizer : A Small Scale Biogas Reactor for a Restaurant

    NARCIS (Netherlands)

    Vasudevan, R.; Karlsson, O.; Dhejne, K.; Derewonko, P.; Brezet, J.C.

    2010-01-01

    The purpose of this study is to determine the technical and economic feasibility of a smallscale bioreactor called the Methanizer for a restaurant. The bioreactor converts organic waste produced by the restaurant into methane. This methane can be used to power the restaurant’s cooking stoves. The

  1. Two-Dimensional Layered Double Hydroxides for Reactions of Methanation and Methane Reforming in C1 Chemistry.

    Science.gov (United States)

    Li, Panpan; Yu, Feng; Altaf, Naveed; Zhu, Mingyuan; Li, Jiangbing; Dai, Bin; Wang, Qiang

    2018-01-31

    CH₄ as the paramount ingredient of natural gas plays an eminent role in C1 chemistry. CH₄ catalytically converted to syngas is a significant route to transmute methane into high value-added chemicals. Moreover, the CO/CO₂ methanation reaction is one of the potent technologies for CO₂ valorization and the coal-derived natural gas production process. Due to the high thermal stability and high extent of dispersion of metallic particles, two-dimensional mixed metal oxides through calcined layered double hydroxides (LDHs) precursors are considered as the suitable supports or catalysts for both the reaction of methanation and methane reforming. The LDHs displayed compositional flexibility, small crystal sizes, high surface area and excellent basic properties. In this paper, we review previous works of LDHs applied in the reaction of both methanation and methane reforming, focus on the LDH-derived catalysts, which exhibit better catalytic performance and thermal stability than conventional catalysts prepared by impregnation method and also discuss the anti-coke ability and anti-sintering ability of LDH-derived catalysts. We believe that LDH-derived catalysts are promising materials in the heterogeneous catalytic field and provide new insight for the design of advance LDH-derived catalysts worthy of future research.

  2. Two-Dimensional Layered Double Hydroxides for Reactions of Methanation and Methane Reforming in C1 Chemistry

    Directory of Open Access Journals (Sweden)

    Panpan Li

    2018-01-01

    Full Text Available CH4 as the paramount ingredient of natural gas plays an eminent role in C1 chemistry. CH4 catalytically converted to syngas is a significant route to transmute methane into high value-added chemicals. Moreover, the CO/CO2 methanation reaction is one of the potent technologies for CO2 valorization and the coal-derived natural gas production process. Due to the high thermal stability and high extent of dispersion of metallic particles, two-dimensional mixed metal oxides through calcined layered double hydroxides (LDHs precursors are considered as the suitable supports or catalysts for both the reaction of methanation and methane reforming. The LDHs displayed compositional flexibility, small crystal sizes, high surface area and excellent basic properties. In this paper, we review previous works of LDHs applied in the reaction of both methanation and methane reforming, focus on the LDH-derived catalysts, which exhibit better catalytic performance and thermal stability than conventional catalysts prepared by impregnation method and also discuss the anti-coke ability and anti-sintering ability of LDH-derived catalysts. We believe that LDH-derived catalysts are promising materials in the heterogeneous catalytic field and provide new insight for the design of advance LDH-derived catalysts worthy of future research.

  3. Biological hydrogen methanation - A review.

    Science.gov (United States)

    Lecker, Bernhard; Illi, Lukas; Lemmer, Andreas; Oechsner, Hans

    2017-12-01

    Surplus energy out of fluctuating energy sources like wind and solar energy is strongly increasing. Biological hydrogen (H 2 ) methanation (BHM) is a highly promising approach to move the type of energy from electricity to natural gas via electrolysis and the subsequent step of the Sabatier-reaction. This review provides an overview of the numerous studies concerning the topic of BHM. The technical and biological parameters regarding the research results of these studies are compared and analyzed hereafter. A holistic view on how to overcome physical limitations of the fermentation process, such as gas-liquid mass transfer or a rise of the pH value, and on the enhancement of environmental circumstances for the bacterial biomass are delivered within. With regards to ex-situ methanation, the evaluated studies show a distinct connection between methane production and the methane percentage in the off-gas. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Microbial electrolysis cells for production of methane from CO2: long-term performance and perspectives

    NARCIS (Netherlands)

    Eerten-Jansen, van M.C.A.A.; Heijne, ter A.; Buisman, C.J.N.; Hamelers, H.V.M.

    2012-01-01

    A methane-producing microbial electrolysis cell (MEC) is a technology to convert CO2 into methane, using electricity as an energy source and microorganisms as the catalyst. A methane-producing MEC provides the possibility to increase the fuel yield per hectare of land area, when the CO2 produced in

  5. Homogeneous catalytic systems for selective oxidation of methane: state of the art

    Directory of Open Access Journals (Sweden)

    Balcer Sylwia

    2015-09-01

    Full Text Available Homogeneous catalysts for methane oxidation are of a particular interest from scientific and economic points of view. The results show a great potential for activation and functionalization of CH bonds of unreactive methane. There are still gaps in the knowledge of how to rationally design catalysts for this process. In this paper state-of-the-art. in methane oxidation homogenous catalysis is presented.

  6. Non-oxidative conversion of methane into higher hydrocarbons over ...

    Indian Academy of Sciences (India)

    Molybdenum impregnated zeolite catalyst has been well-known for methane conversion into higher hydrocarbons under non-oxidative condition. HZSM-5 & HMCM-22 zeolites are the effective supports for this purpose. However, the catalytic performance of HMCM-22 supported molybdenum catalyst is consideredsuitable ...

  7. Bifunctional cobalt F-T catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.G.; Coughlin, P.K.; Yang, C.L.; Rabo, J.A.

    1986-03-01

    Results on the catalytic screening of Fischer-Tropsch catalysts containing shape selective components are reported. Catalysts consist of promoted cobalt intimately contacted with Union Carbide molecular sieves and were tested using a Berty type internally recycled reactor. Methods of preparation, promoters and shape selective components were varied and aimed at improving catalyst performance. Catalysts were developed demonstrating high C/sub 5/ + yields with high olefin content and low methane production while maintaining stability under both low and high H/sub 2/:CO ratio conditions.

  8. Influence of potassium on the competition between methane and ethane in steam reforming over Pt supported on yttrium-stabilized zirconia.

    NARCIS (Netherlands)

    Graf, P.O.; Mojet, Barbara; Lefferts, Leonardus

    2008-01-01

    effect of addition of potassium to Pt supported on yttrium-stabilized zirconia (PtYSZ) catalyst for steam reforming of methane, ethane and methane/ethane mixtures was explored. Addition of potassium has a positive effect on preferential steam reforming of methane in mixtures of methane and ethane

  9. 'Methane oxidation on supported gold catalysts'

    DEFF Research Database (Denmark)

    Walther, Guido

    2008-01-01

    the energy stored in the molecule available, is a major research challenge. In this PhD thesis, CH4 oxidation on nanoparticular gold is studied both experimentally and theoretically. In the course of this PhD project, CH4 oxidation was experimentally found more likely to form CO2 and H2O than other low index...... steady-state activity measurements were performed to obtain the reaction rates for CO and H2 oxidation. These reactions were studied on three different gold particle sizes using either O2 or N2O as oxidation agents. Using particle size distributions obtained from TEM analysis, it was found that the CO...

  10. Landfill Methane

    Science.gov (United States)

    Landfill methane (CH4) accounts for approximately 1.3% (0.6 Gt) of global anthropogenic greenhouse gas emissions relative to total emissions from all sectors of about 49 Gt CO2-eq yr-1. For countries with a history of controlled landfilling, landfills can be one of the larger national sources of ant...

  11. Sabatier Catalyst Poisoning Investigation

    Science.gov (United States)

    Nallette, Tim; Perry, Jay; Abney, Morgan; Knox, Jim; Goldblatt, Loel

    2013-01-01

    The Carbon Dioxide Reduction Assembly (CRA) on the International Space Station (ISS) has been operational since 2010. The CRA uses a Sabatier reactor to produce water and methane by reaction of the metabolic CO2 scrubbed from the cabin air and the hydrogen byproduct from the water electrolysis system used for metabolic oxygen generation. Incorporating the CRA into the overall air revitalization system has facilitated life support system loop closure on the ISS reducing resupply logistics and thereby enhancing longer term missions. The CRA utilizes CO2 which has been adsorbed in a 5A molecular sieve within the Carbon Dioxide Removal Assembly, CDRA. There is a potential of compounds with molecular dimensions similar to, or less than CO2 to also be adsorbed. In this fashion trace contaminants may be concentrated within the CDRA and subsequently desorbed with the CO2 to the CRA. Currently, there is no provision to remove contaminants prior to entering the Sabatier catalyst bed. The risk associated with this is potential catalyst degradation due to trace organic contaminants in the CRA carbon dioxide feed acting as catalyst poisons. To better understand this risk, United Technologies Aerospace System (UTAS) has teamed with MSFC to investigate the impact of various trace contaminants on the CRA catalyst performance at relative ISS cabin air concentrations and at about 200/400 times of ISS concentrations, representative of the potential concentrating effect of the CDRA molecular sieve. This paper summarizes our initial assessment results.

  12. High-Activity Dealloyed Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kongkanand, Anusorn [General Motors LLC, Pontiac, MI (United States)

    2014-09-30

    Reduction of costly Pt usage in proton exchange membrane fuel cell electrodes is one of the major challenges towards development and commercialization of fuel cell vehicles. Although few have met the initial-kinetic activity requirements in a realistic fuel cell device, no catalyst material has ever met the demanding fuel cell durability targets set by DOE. In this project, a team of 4 universities and 2 companies came together to investigate a concept that appeared promising in preliminary non-fuel cell tests then to further develop the catalyst to a mature level ready for vehicle implementation. The team consists of academia with technical leadership in their respective areas, a catalyst supplier, and a fuel cell system integrator.The tightly collaborative project enabled development of a highly active and durable catalyst with performance that significantly exceeds that of previous catalysts and meets the DOE targets for the first time (Figure 1A). The catalyst was then further evaluated in full-active-area stack in a realistic vehicle operating condition (Figure 1B). This is the first public demonstration that one can realize the performance benefit and Pt cost reduction over a conventional pure Pt catalyst in a long-term realistic PEMFC system. Furthermore, systematic analyses of a range of catalysts with different performance after fuel cell testing allowed for correlation between catalyst microstructure and its electrocatalytic activity and durability. This will in turn aid future catalyst development.

  13. Investigation of sulfur-tolerant catalysts for selective synthesis of hydrocarbon liquids from coal-derived gases. Quarterly technical progress report, September 19-December 18, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Bartholomew, C H

    1981-01-10

    A 15% iron boride on SiO/sub 2/ catalyst was prepared using an alcohol solution reduction with NaBH/sub 4/. H/sub 2/ chemisorption measurements were performed for Fe-S-100 (3% Fe/SlO/sub 2/) and are in progress for the iron-boride-silica catalyst. Reduction of Co catalysts at 623 K rather than 723 K is being tested as a method to improve dispersion by decreasing the amount of Co-support interaction. An in depth study of non olefinic and nonparaffinic compound retention times on the 10% SP2100 chromotograph column has shown that the compounds elute in the following order for a specific carbon number: alkene < alkane < aldehyde < ketone < ester < alcohol < acid. Mass flow controllers have been installed in the reactor system and are fully operational.

  14. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

    Directory of Open Access Journals (Sweden)

    Bernardo Castro-Dominguez

    2016-09-01

    Full Text Available Palladium-based catalytic membrane reactors (CMRs effectively remove H2 to induce higher conversions in methane steam reforming (MSR and water-gas-shift reactions (WGS. Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i a conventional packed bed reactor packed (PBR for MSR, (ii a PBR with five layers of two catalysts in series and (iii a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields.

  15. A novel magnetically recyclable heterogeneous catalyst for the

    Indian Academy of Sciences (India)

    Nano -propylsulphonated -Fe2O3 (NPS--Fe2O3) was applied as a new magnetically recyclable heterogeneous catalyst for the efficient one-pot synthesis of bis(pyrazolyl)methanes in water. The catalyst was easily isolated from the reaction mixture by a magnetic bar and reused at least five times without significant ...

  16. Coalbed Methane Outreach Program

    Science.gov (United States)

    Coalbed Methane Outreach Program, voluntary program seeking to reduce methane emissions from coal mining activities. CMOP promotes profitable recovery/use of coal mine methane (CMM), addressing barriers to using CMM instead of emitting it to atmosphere.

  17. Decarbonisation of fossil energy via methane pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Kreysa, G.; Agar, D.W.; Schultz, I. [Technische Univ. Dortmund (Germany)

    2010-12-30

    Despite the rising consumption of energy over the last few decades, the proven reserves of fossil fuels have steadily increased. Additionally, there are potentially tremendous reserves of methane hydrates available, which remain to be exploited. The use of fossil energy sources is thus increasingly being dictated less by supply than by the environmental concerns raised by climate change. In the context of the decarbonisation of the global energy system that this has stimulated, new means must be explored for using methane as energy source. Noncatalytic thermal pyrolysis of methane is proposed here as a promising concept for utilising methane with low to zero carbon dioxide emissions. Following cracking, only the energy content of the hydrogen is used, while the carbon can be stored safely and retrievably in disused coal mines. The thermodynamics and different process engineering concepts for the technical realisation of such a carbon moratorium technology are discussed. The possible contribution of methane pyrolysis to carbon negative geoengineering is also addressed. (orig.)

  18. Direct catalytic conversion of methane and light hydrocarbon gases. Quarterly report No. 5, November 16, 1987--January 15, 1988

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, R.B. Jr.; Chan Yee Wai

    1988-02-05

    The goal of this research is to develop catalysts that directly convert methane and light hydrocarbons to intermediates that later can be converted to either liquid fuels or value-added chemicals, as economics dictate. During this reporting period, we have synthesized and tested several novel catalysts for methane reforming (Tasks 1 and 2) and for partial oxidation of methane (Tasks 3 and 4). We started to test a mixed metal system, an FeRu{sub 3} cluster. This catalyst was supported both on zeolite and on magnesium oxide and the systems were tested for methane reforming at various reaction temperatures. We also prepared and tested a monomeric ruthenium catalyst supported on magnesium oxide. We found that methane is activated at a lower temperature with the basic magnesium oxide support than with acidic supports such as zeolite or alumina. Methane conversions increased with temperature, but the production of coke also increased. We prepared a sterically hindered ruthenium porphyrin encapsulated in a zeolite supercage for catalysis of methane oxidation. The results showed that only carbon dioxide was produced. Addition of axial base to this catalyst gave similar results. Another type of catalyst, cobalt Schiff base complexes, was also prepared and tested for methane oxidation. In this case, no methane conversion was observed at temperatures ranging from 200 to 450{degrees}C. These complexes do not appear to be stable under the reaction conditions.

  19. Realization of a technical and economic referential of units of organic waste processing by methanization with and without biogas valorization. Study report; Realisation d'un referentiel technique et economique d'unites de traitement de dechets organiques par methanisation avec et sans valorisation du biogaz. Rapport d'etude

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2010-07-01

    Based on a literature survey and on the analysis of results obtained in operating installations in different countries (Germany, Denmark, France, Netherlands, and Switzerland), this study concerns the methanization of different substrates: domestic wastes, sludge from sewage processing plants, industrial wastes and effluents, agricultural wastes and effluents. This synthetic report describes the current status of methanization in terms of regulatory framework (for renewable energies, and for waste management, digestion residues and compost valorization in Europe and in the studied countries), and in terms of actual production and variety of base products. It gives an overview of the available technical solutions, of the products they use, and of the associated investment costs. These techniques are: completely stirred tank reactor (SCTR), upflow anaerobic sludge blanket (UASB), internal circulation (IC), 'piston', batch, percolation, contact, fluidized bed, and anaerobic filter. It reports a synthesis of answers given to a questionnaire about technical and economic aspects

  20. Methane emissions from coal mining

    International Nuclear Information System (INIS)

    Williams, A.; Mitchell, C.

    1993-01-01

    This paper outlines some of the problems associated with the prediction of levels of methane emission from underground and surface coal mines. Current knowledge of coal mining emissions sources is outlined. On the basis of this information the methodology proposed by the IPCC/OECD Programme on National Inventories is critically examined and alternatives considered. Finally, the technical options for emissions control are examined together with their feasibility. 8 refs., 6 figs., 2 tabs

  1. Thermocatalytic decomposition of methane/methanol mixture for hydrogen production: Effect of nickel loadings on alumina support

    Science.gov (United States)

    Awad, Ali; Salam, Abdus; Abdullah, Bawadi

    2017-10-01

    Hydrogen produced by thermocatalytic decomposition of methane is termed as clean and alternative fuel however high reaction temperature and fast catalyst deactivation limitize the efficiency of this process. In this study nickel based catalyst supported on alumina with various Ni loadings were prepared by impregnation method and employed for TCD of methane/methanol mixture for hydrogen production. Surface area and pore volume were decreased by increasing the amount of nickel loading on alumina. The results revealed that both reaction temperature and nickel loading affected the reaction rates and catalyst deactivation time. Scanning electron microscope (SEM) and Thermogravematric analysis (TGA) were used for characterization of fresh and spent catalyst. Crystalline carbon was formed on the surface of the catalyst and was proved by TGA analysis. Methane yield increased as the reaction temperature was increased but the catalyst deactivation time was decreased as a lot carbon was encapsulated on the surface of the catalyst.

  2. Direct conversion of methane to C sub 2 's and liquid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Warren, B.K.; Campbell, K.D.

    1989-11-22

    Objectives of the project are to discover and evaluate novel catalytic systems for the conversion of methane or by-product light hydrocarbon gases either indirectly (through intermediate light gases rich in C{sub 2}'s) or directly to liquid hydrocarbon fuels, and to evaluate, from an engineering perspective, different conceptualized schemes. The approach is to carry out catalyst testing on several specific classes of potential catalysts for the conversion of methane selectively to C{sub 2} products. Promoted metal oxide catalysts were tested. Several of these exhibited similar high ethylene to ethane ratios and low carbon dioxide to carbon monoxide ratios observed for the NaCl/{alpha}-alumina catalyst system reported earlier. Research on catalysts containing potentially activated metals began with testing of metal molecular sieves. Silver catalysts were shown to be promising as low temperature catalysts. Perovskites were tested as potential methane coupling catalysts. A layered perovskite (K{sub 2}La{sub 2}Ti{sub 3}O{sub 10}) gave the highest C{sub 2} yield. Work continued on the economic evaluation of a hypothetical process converting methane to ethylene. An engineering model of the methane coupling system has been prepared. 47 refs., 17 figs., 57 tabs.

  3. Selective Coke Combustion by Oxygen Pulsing During Mo/ZSM-5-Catalyzed Methane Dehydroaromatization

    NARCIS (Netherlands)

    Kosinov, Nikolay; Coumans, Ferdy J A G; Uslamin, Evgeny; Kapteijn, F.; Hensen, Emiel J M

    2016-01-01

    Non-oxidative methane dehydroaromatization is a promising reaction to directly convert natural gas into aromatic hydrocarbons and hydrogen. Commercialization of this technology is hampered by rapid catalyst deactivation because of coking. A novel approach is presented involving selective

  4. Historical methane hydrate project review

    Science.gov (United States)

    Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

    2013-01-01

    In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas hydrates represent both a scientific and technical challenge and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated

  5. Methane activation on palladium and mercury loaded solid supports

    Energy Technology Data Exchange (ETDEWEB)

    Kataja, K.; Huuska, M.; Karinto, K.; Maijanen, A.; Reinikainen, M.; Kiviaho, J.; Hase, A. [VTT Chemical Technology, Espoo (Finland)

    1996-12-31

    Methane activation by non-radical method and especially possibilities to heterogenize the homogeneous non-radical system of Periana et al. was studied. Varied loadings of Pd and Hg were ion exchanged to acidic ZSM-5 zeolites with two different Si/A1 ratios. Activation was tested in tubular flow reactor and the outcoming gas was analyzed with quadrupole mass spectrometer. Catalysts, fresh and used, were characterized by XRF and XRD spectroscopies. The methane activation was observed on tested catalysts. However, the activation was concluded to occur mainly through radical reaction and only to some extent by the expected non-radical mechanism. (author) (9 refs.)

  6. Non-Faradaic electrochemical promotion of catalytic methane reforming for methanol production

    Science.gov (United States)

    Fan, Qinbai

    2016-11-22

    A method of converting methane to methanol at low temperatures utilizes a reactor including an anode, a cathode, a membrane separator between the anode and cathode, a metal oxide catalyst at the anode and a hydrogen recovery catalyst at the cathode. The method can convert methane to methanol at as rate exceeding the theoretical Faradaic rate due to the contribution of an electrochemical reaction occurring in tandem with a Faradaic reaction.

  7. Plasma catalytic process for CO2 methanation

    International Nuclear Information System (INIS)

    Nizio, Magdalena

    2016-01-01

    The limited resources of oil and natural gas, together with an increasing energy demand, forces us to seek more and more efficient and cleaner energy production alternatives. Hydrogen has been recently considered as a promising energy carrier. However, there are several inherent problems to the utilization of H 2 , from its transportation to its distribution. Transformation of the H 2 molecule by fixing into a carbon-containing compound, i.e. CH 4 , will offer the possibility of using the conventional transportation network. Indeed, the Sabatier reaction, which is highly exothermic, involves the reaction of carbon dioxide and hydrogen gas in order to produce methane and water. This process, called methanation, represents a feasible approach contributing to the reduction of the CO 2 emissions in our atmosphere, through a closed carbon cycle involving the valorization of CO 2 , i.e. from capture. However, below a temperature of 250 C, the conversion becomes practically close to 0 %, whereas at higher temperatures, i.e., (≥300 C), the co-existence of secondary reactions favours the formation of CO and H 2 . This is the reason why new catalysts and process conditions are continuously being investigated in order to maximize the methane selectivity at low reaction temperatures at atmospheric pressure. Therefore, by using catalysts combined to Dielectric Barrier Discharge plasmas (DBD), the activation of the methanation reaction can be enhanced and overcome the drawbacks of existing conventional processes. Several Ni-containing catalysts were prepared using various ceria-zirconia oxides as supports, with different Ce/Zr ratios. The results obtained in the adiabatic conditions at low temperatures (ranging between 100-150 C), in the presence of catalysts activated by plasma, are promising. Indeed, the conversion of CO 2 to CH 4 is about 85 % with a selectivity close to 100 %. The same conversion in the absence of the plasma activation of the catalyst is observed at 350 C

  8. Technical characterisation of different catalysts for the selective reduction of nitrogen oxides in fluegas. Reaktionstechnische Charakterisierung unterschiedlicher Katalysatoren zur selektiven Reduktion von Stickoxiden in Rauchgasen

    Energy Technology Data Exchange (ETDEWEB)

    Dembele, C.

    1993-11-26

    In the context of this work, experimental investigations were made on the kinetics of the selective catalytic reduction of nitrogen monoxide with ammonia on catalysts of industrial origin. The aim of the work was to examine the effect of NO, NH[sub 3], H[sub 2]O and SO[sub 2] concentrations and the temperature on the speed of material quantity change of NO. The measurements with water proved difficult, as with high water contents, there was a drift of the measured values of NO concentration, the cause of which could not be cleared up. By repeated calibration of the NO concentrations to be set in the waste gas during a series of measurements, success was achieved in compensating for this drift and in obtaining reproducible results. The addition of SO[sub 2] to the reaction mixture brings the simulated fluegas closer to real powerstation fluegas. In determining the NO and NH[sub 3] concentration, the 'quenching' effect occurred and the calibration of the chemi-luminescence equipment frequently had to be repeated. The limited partial step of the reduction of NO is the transports of the educts into the pores of the catalyst grain to the active centres. (orig./EF)

  9. Síntese e caracterização de perovskitas LaNi(1-xCo xO3 como precursores de catalisadores para a conversão do metano a gás de síntese pela reforma com CO2 Preparation and characterization of LaNi(1-xCo xO3 perovskites as catalyst precursors for synthesis gas generation by CO2 reforming of methane

    Directory of Open Access Journals (Sweden)

    Sania Maria de Lima

    2007-04-01

    Full Text Available LaNiO3 perovskite was modified by partial substitution of nickel by cobalt in order to increase the stability and resistance to carbon deposition during the methane CO2 reforming. The results showed that a suitable combination of precipitation and calcination steps resulted in oxides with the desired structure and with important properties for application in heterogeneous catalysis. The partial substitution of Ni by Co resulted in lower rates of conversion of both the reactants, but the catalyst stability was highly increased. The LaNi0.3Co0.7O3 catalyst, calcined at 800 ºC, was the most active under the reaction conditions.

  10. Methane hydrates in nature - Current knowledge and challenges

    Science.gov (United States)

    Collett, Timothy S.

    2014-01-01

    Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

  11. Final Scientific/Technical Report for project “Increasing the Rate and Extent of Microbial Coal to Methane Conversion through Optimization of Microbial Activity, Thermodynamics, and Reactive Transport”

    Energy Technology Data Exchange (ETDEWEB)

    Fields, Matthew [Montana State Univ., Bozeman, MT (United States)

    2018-01-17

    Currently, coal bed methane (CBM) wells have a limited lifetime since the rate of methane removal via the installed wells is much faster than the in situ methane production rates. Along with water issues created by large amounts of CBM production water, the short life span of CBM wells is a huge deterrent to the environmental and economic feasibility of CBM production. The process of biogenic methanogenesis can be enhanced via the stimulation of the associated microbial communities that can convert the organic fractions of coal to methane. This process is termed Microbially-Enhanced Coal Bed Methane (MECBM). However, the rates of methane production are still limited and long incubation times are necessary. We hypothesized that the elucidation of chemical and biological parameters that limited MECBM together with thermodynamic considerations would inform strategies to optimize the process under flow conditions. We incorporated microbiological, physicochemical, and engineering processes to develop a more sustainable CBM production scheme with native coal and native microorganisms. The proposed combination of microbial ecology and physiology as well as optimized engineering principles minimized key constraints that impact microbial coal conversion to methane under environmentally relevant conditions. The combined approach for bench-scale tests resulted in more effective and less environmentally burdensome coal-dependent methane production with the potential for H2O and CO2 management.

  12. Methane splitting in the K plant at Heydebreck

    Energy Technology Data Exchange (ETDEWEB)

    1942-03-09

    This report consisted of two major topics. The first was methane splitting in equipment for gas for distant transmission. The amount to be split was 3500 m/sup 3//hr methane per system. The temperature in the converter outlet was 850/sup 0/C and the methane was preheated to 650/sup 0/C. The results of this showed oxygen requirements to be 0.487 m/sup 3//m/sup 3/ of methane, steam requirements to be 0.529 kg/m/sup 3/ of methane, condensate requirements to be 0.518 kg/m/sup 3/ of methane, and cooling-water requirements to be 16 kg/m/sup 3/ of methane. The second topic was methane splitting in equipment for long-distance gas with additional indirect cooling. A summary showed the oxygen requirements to be 0.487 m/sup 3//m/sup 3/ of methane, steam requirements to be 0.107 kg/m/sup 3/ of methane, condensate requirements to be 0.526 kg/m/sup 3/ of methane, and cooling-water requirements to be 9.6 kg/m/sup 3/ of methane. The items discussed for each topic included calculations of methane converters, which included oxygen requirements and a heat balance of the converter; cooling of the split gas, which included heat content of the split gas at the catalyst converter outlet and heat exchangers; and the cooler-vaporizer system, which included a heat balance of the water circuit, determination of the amount of water in the cooler-vaporizer, and final cooling. 3 figures.

  13. Kinetics of methane steam reforming over Ni/Ce-ZrO2

    International Nuclear Information System (INIS)

    Laosiripojana, N.; Assabumrungrat, S.

    2004-01-01

    'Full text:' This paper investigates the steam reforming of methane over Ni catalyst on Ce-ZrO2 support with different Ce/Zr ratios. Firstly, the pretreatment conditions of each catalyst were investigated in order to provide the best performance toward methane steam reforming. Ni/Ce- ZrO2 with the Ce/Zr ratio of 3/1 showed the best performance in terms of activity and stability. Essential kinetic information for this catalyst was determined. The reaction order in methane was always 1. The catalyst showed a positive effect of hydrogen and a negative effect of steam on the methane steam reforming reactivity. The negative effect of steam became weaker with increasing hydrogen partial pressure and temperature, whereas the positive effect of hydrogen became slightly stronger with increasing steam partial pressure but seemed to be independent of temperature. Addition of carbon monoxide promoted the conversion of methane, whereas addition of carbon dioxide inhibited the reforming rate. Methane steam reforming mechanism proposed by Boudart et al. (1972) can be applied to explain the experimental results for the steam reforming of methane over Ni/Ce-ZrO2. In addition, the experimental data can be well fitted to the methane steam reforming rate equation reported by Dick et al. (2000). (author)

  14. Catalysts preparing

    International Nuclear Information System (INIS)

    Normatov, I.Sh.; Mirsaidov, U.M.

    2003-01-01

    One of the base area of zeolites industry using is catalysis. The catalytic properties of zeolites use in the carbonated reactions in the petrochemistry. Last years zeolite catalysts use in oxidative-reduction processes

  15. Lunar CATALYST

    Data.gov (United States)

    National Aeronautics and Space Administration — Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) is a NASA initiative to encourage the development of U.S. private-sector robotic lunar...

  16. Photo-oxidation catalysts

    Science.gov (United States)

    Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  17. Synthesis of Supported Bimetal Catalysts using Galvanic Deposition Method.

    Science.gov (United States)

    Mahara, Yuji; Ohyama, Junya; Sawabe, Kyoichi; Satsuma, Atsushi

    2018-02-22

    Supported bimetallic catalysts have been studied because of their enhanced catalytic properties due to metal-metal interactions compared with monometallic catalysts. We focused on galvanic deposition (GD) as a bimetallization method, which achieves well-defined metal-metal interfaces by exchanging heterogeneous metals with different ionisation tendencies. We have developed Ni@Ag/SiO 2 catalysts for CO oxidation, Co@Ru/Al 2 O 3 catalysts for automotive three-way reactions and Pd-Co/Al 2 O 3 catalysts for methane combustion by using the GD method. In all cases, the catalysts prepared by the GD method showed higher catalytic activity than the corresponding monometallic and bimetallic catalysts prepared by the conventional co-impregnation method. The GD method provides contact between noble and base metals to improve the electronic state, surface structure and reducibility of noble metals. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Catalisadores sol-gel de Ni-SiO2 e Ni-Al2O3 aplicados na reforma de metano com CO2 = Ni-SiO2 and Ni-Al2O3 sol-gel catalysts applied to methane reforming with CO2

    Directory of Open Access Journals (Sweden)

    Giane Gonçalves

    2005-01-01

    Full Text Available A reação de reforma do metano com CO2 apresenta-se como um processopromissor de geração de gás de síntese e hidrogênio. Neste sentido, foram preparados catalisadores de níquel-sílica e níquel-alumina pelo método sol-gel, com carga metálica nominal de 8% em massa. Os catalisadores foram caracterizados por redução à temperatura programada, análise termogravimétrica e determinação da área superficial específica. A reação de reforma do metano com CO2 foi realizada em um micro-reator contendo 500 mg de catalisador, previamente ativado em uma mistura redutora contendo hidrogênio. Osensaios de reforma a seco do metano foram realizados a 800°C, na pressão atmosférica, por um período de 12 horas, com uma razão molar de alimentação de [CO2:CH4] = 6. Os produtos da reação foram analisados por cromatografia gasosa. Dentre os catalisadoresavaliados, nas condições de reação estudadas, o catalisador de níquel suportado em sílica foi o que apresentou o melhor desempenho.The dry reforming reaction of methane comes as a promising process of syngas and hydrogen. Nickel catalysts on Al2O3 and SiO2 were synthesized by sol-gel method, with metalic load of 8% weight. The catalysts were characterized by temperature programmed reduction (TPR, termogravimetry analysis (TGA and specific surface area measurements (BET. The dry reforming reaction was performed in a micro reactor packed with 500 mg of catalyst, previously activated in atmosphere of hydrogen. The dry reforming tests were done at 800oC and atmospheric pressure by a period of 12 hours, with a molar ratio in the feeding of [CO2:CH4] = 6. The products of the reaction were analyzed by gas chromatograph. The Ni-SiO2 catalysts showed better performance.

  19. Towards an energy self-sufficiency of territories. methanization and biogas, a sector with a bright future

    International Nuclear Information System (INIS)

    Ceron, Pascale; Gorges, Pascale; Cazas, Judith; Dolivet, Sophie; Guy, Lionel; Jacob, Antoine; Schlienger, Marc; Eberhardt, Mathieu

    2012-10-01

    These both publications present and describe methanization, the different models of projects or installations, and the valorisation of products, propose a focus on heat network and co-generation, and on bio-methane and injection, and outline the benefits of methanization. They also propose a set of questions and answers related to technical, social or environmental issues raised by methanization and methanization projects, and present various projects located in different places in France while indicating some key figures for them

  20. Catalysts for improved fuel processing

    Energy Technology Data Exchange (ETDEWEB)

    Borup, R.L.; Inbody, M.A. [and others

    2000-09-01

    This report covers our technical progress on fuel processing catalyst characterization for the specific purpose of hydrogen production for proton-exchange-membrane (PEM) fuel cells. These development efforts support DOE activities in the development of compact, transient capable reformers for on-board hydrogen generation starting from candidate fuels. The long-term objective includes increased durability and lifetime, in addition to smaller volume, improved performance, and other specifications required meeting fuel processor goals. The technical barriers of compact fuel processor size, transient capability, and compact, efficient thermal management all are functions of catalyst performance. Significantly, work at LANL now tests large-scale fuel processors for performance and durability, as influenced by fuels and fuel constituents, and complements that testing with micro-scale catalyst evaluation which is accomplished under well controlled conditions.

  1. Operando chemistry of catalyst surfaces during catalysis.

    Science.gov (United States)

    Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A; Wang, Nan; Fu, Wensheng; Tao, Franklin Feng

    2017-04-03

    Chemistry of a catalyst surface during catalysis is crucial for a fundamental understanding of mechanism of a catalytic reaction performed on the catalyst in the gas or liquid phase. Due to the pressure- or molecular density-dependent entropy contribution of gas or liquid phase of the reactants and the potential formation of a catalyst surface during catalysis different from that observed in an ex situ condition, the characterization of the surface of a catalyst under reaction conditions and during catalysis can be significant and even necessary for understanding the catalytic mechanism at a molecular level. Electron-based analytical techniques are challenging for studying catalyst nanoparticles in the gas or liquid phase although they are necessary techniques to employ. Instrumentation and further development of these electron-based techniques have now made in situ/operando studies of catalysts possible. New insights into the chemistry and structure of catalyst nanoparticles have been uncovered over the last decades. Herein, the origin of the differences between ex situ and in situ/operando studies of catalysts, and the technical challenges faced as well as the corresponding instrumentation and innovations utilized for characterizing catalysts under reaction conditions and during catalysis, are discussed. The restructuring of catalyst surfaces driven by the pressure of reactant(s) around a catalyst, restructuring in reactant(s) driven by reaction temperature and restructuring during catalysis are also reviewed herein. The remaining challenges and possible solutions are briefly discussed.

  2. Conversion of methane to higher hydrocarbons (Biomimetic catalysis of the conversion of methane to methanol). Final report

    Energy Technology Data Exchange (ETDEWEB)

    Watkins, B.E.; Taylor, R.T.; Satcher, J.H. [and others

    1993-09-01

    In addition to inorganic catalysts that react with methane, it is well-known that a select group of aerobic soil/water bacteria called methanotrophs can efficiently and selectively utilize methane as the sole source of their energy and carbon for cellular growth. The first reaction in this metabolic pathway is catalyzed by the enzyme methane monooxygenase (MMO) forming methanol. Methanol is a technology important product from this partial oxidation of methane since it can be easily converted to liquid hydrocarbon transportation fuels (gasoline), used directly as a liquid fuel or fuel additive itself, or serve as a feedstock for chemicals production. This naturally occurring biocatalyst (MMO) is accomplishing a technologically important transformation (methane directly to methanol) for which there is currently no analogous chemical (non-biological) process. The authors approach has been to use the biocatalyst, MMO, as the initial focus in the development of discrete chemical catalysts (biomimetic complexes) for methane conversion. The advantage of this approach is that it exploits a biocatalytic system already performing a desired transformation of methane. In addition, this approach generated needed new experimental information on catalyst structure and function in order to develop new catalysts rationally and systematically. The first task is a comparative mechanistic, biochemical, and spectroscopic investigation of MMO enzyme systems. This work was directed at developing a description of the structure and function of the catalytically active sites in sufficient detail to generate a biomimetic material. The second task involves the synthesis, characterization, and chemical reactions of discrete complexes that mimic the enzymatic active site. These complexes were synthesized based on their best current understanding of the MMO active site structure.

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

    NARCIS (Netherlands)

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

    2009-01-01

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

  4. Technical, economic, environmental and social follow-up of innovating farm-based small methanization plants: BIOGAZ PLUS - Report after a 12-month follow-up; Installation: EARL Guilbaud - Report after a 15-month follow-up; Installation: GAEC Des Buissons - Report after a 12-month follow-up

    International Nuclear Information System (INIS)

    Lalanne, Mathieu; Cordelier, Marine; Pouech, Philippe; Thual, Julien; Bastide, Guillaume; Faure, Benoit; Faure, Jean-Marie; Bousquet, Dominique; El Habti, Audrey; L'Heriau, Germain; Guianvarch, David; Farcy, Alexandre; Banville, Sandrine; Chauvin, Damien; Frederic, Sylvain; Haumont, Francois; Guilbaud, Gerard; Leroux, Yannick; Tronc, Jean-Sebastien; Menard, Anthony

    2015-08-01

    This document contains three follow-up reports, each concerning a small farm-based methanization unit. For each one, the report proposes a technical description (operation, provisional exploitation assessment, process principle and implementation, installed instrumentation), describes the status of production (noticed dysfunctions and identified causes, returns on experience), an operation assessment after 12 or 15 months in terms of biological performance (composition of input mixture, methane generation potential, organic load) and energetic performance (biogas, electric, thermal and energetic assessments), an assessment of environmental and social performance (time spent, energy efficiency, greenhouse gas assessment, integration of the installation within the farm, risk and pollution assessment), an economic assessment in terms of investment, of operating statements and of indicators of financial profitability. Results of composition measurements performed on input materials and digestates are provided

  5. Global Methane Initiative

    Science.gov (United States)

    The Global Methane Initiative promotes cost-effective, near-term methane recovery through partnerships between developed and developing countries, with participation from the private sector, development banks, and nongovernmental organizations.

  6. 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.

  7. The Methanizer: A Small Scale Biogas Reactor for a Restaurant

    OpenAIRE

    Vasudevan, R.; Karlsson, O.; Dhejne, K.; Derewonko, P.; Brezet, J.C.

    2010-01-01

    The purpose of this study is to determine the technical and economic feasibility of a smallscale bioreactor called the Methanizer for a restaurant. The bioreactor converts organic waste produced by the restaurant into methane. This methane can be used to power the restaurant’s cooking stoves. The system proposed is a double-tank, batch-fed bioreactor. This product will help reduce the need for natural gas as well as cut down on landfill use. Results from the technical analysis showed that the...

  8. Highly dispersed metal catalyst

    Science.gov (United States)

    Xiao, Xin; West, William L.; Rhodes, William D.

    2016-11-08

    A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.

  9. methanes using Expanded Perlite-PPA as a heterogeneous solid ...

    Indian Academy of Sciences (India)

    Nadkarni S V, Gawande M B, Jayaram R V and. Nagarkar J M 2008 Synthesis of bis(indolyl)methanes catalyzed by surface modified zirconia Catal. Commun. 9 1728. 28. Satam J R, Parghi K D and Jayaram R V 2008 12-. Tungstophosphoric acid supported on zirconia as an effi- cient and heterogeneous catalyst for the ...

  10. Bi-layer functionally gradient thick film semiconducting methane ...

    Indian Academy of Sciences (India)

    Gas sensors based on metal oxide semiconductors like tin dioxide are widely used for the detection of toxic and combustible gases like carbon monoxide, methane and LPG. One of the problems of such sensors is their lack of sensitivity, which to some extent, can be circumvented by using different catalysts. However, highly ...

  11. Methane and carbon dioxide ratio in excreted air for quantification of the methane production from ruminants

    DEFF Research Database (Denmark)

    Madsen, Jørgen; Bjerg, Bjarne Schmidt; Hvelplund, Torben

    2010-01-01

    This technical note presents a simple, fast, reliable and cheap method to estimate the methane (CH4) production from animals by using the CH4 and carbon dioxide (CO2) concentrations in air near the animals combined with an estimation of the total CO2 production from information on intake of metab......This technical note presents a simple, fast, reliable and cheap method to estimate the methane (CH4) production from animals by using the CH4 and carbon dioxide (CO2) concentrations in air near the animals combined with an estimation of the total CO2 production from information on intake...

  12. Brominated methanes as photoresponsive molecular storage of elemental Br2.

    Science.gov (United States)

    Kawakami, Kazumitsu; Tsuda, Akihiko

    2012-10-01

    The photochemical generation of elemental Br(2) from brominated methanes is reported. Br(2) was generated by the vaporization of carbon oxides and HBr through oxidative photodecomposition of brominated methanes under a 20 W low-pressure mercury lamp, wherein the amount and situations of Br(2) generation were photochemically controllable. Liquid CH(2)Br(2) can be used not only as an organic solvent but also for the photoresponsive molecular storage of Br(2), which is of great technical benefit in a variety of organic syntheses and in materials science. By taking advantage of the in situ generation of Br(2) from the organic solvent itself, many organobromine compounds were synthesized in high practical yields with or without the addition of a catalyst. Herein, Br(2) that was generated by the photodecomposition of CH(2)Br(2) retained its reactivity in solution to undergo essentially the same reactions as those that were carried out with solutions of Br(2) dissolved in CH(2)Br(2) that were prepared without photoirradiation. Furthermore, HBr, which was generated during the course of the photodecomposition of CH(2)Br(2), was also available for the substitution of the OH group for the Br group and for the preparation of the HBr salts of amines. Furthermore, the photochemical generation of Br(2) from CH(2)Br(2) was available for the area-selective photochemical bleaching of natural colored plants, such as red rose petals, wherein Br(2) that was generated photochemically from CH(2)Br(2) was painted onto the petal to cause radical oxidations of the chromophoric anthocyanin molecules. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Syngas production by CO₂ reforming of methane over Co/Mg Ni x ...

    Indian Academy of Sciences (India)

    Keywords. Synthesis gas; H₂ production; dry-reforming of biogas; MgO-NiO catalyst. Abstract. By using catalysts of Co/Mg1−xNixO (x= 0, 0.03, 0.07, 0.15; 1 wt% Co each), we performed the dry reforming of methane. The catalysts were prepared by K ₂ CO ₃ co-precipitation from aqueous nickel nitrate hexahydrate and ...

  14. Methane Hydrates: Chapter 8

    Science.gov (United States)

    Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott

    2008-01-01

    Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be

  15. Bimetal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ng, K. Y. Simon; Salley, Steve O.; Wang, Huali

    2017-10-03

    A catalyst comprises a carbide or nitride of a metal and a promoter element. The metal is selected from the group consisting of Mo, W, Co, Fe, Rh or Mn, and the promoter element is selected from the group consisting of Ni, Co, Al, Si, S or P, provided that the metal and the promoter element are different. The catalyst also comprises a mesoporous support having a surface area of at least about 170 m.sup.2 g.sup.-1, wherein the carbide or nitride of the metal and the promoter element is supported by the mesoporous support, and is in a non-sulfided form and in an amorphous form.

  16. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal

    2014-01-01

    How can architecture promote the enriching experiences of the tolerant, the democratic, and the learning city - a city worth living in, worth supporting and worth investing in? Catalyst Architecture comprises architectural projects, which, by virtue of their location, context and their combination...... of programs, have a role in mediating positive social and/or cultural development. In this sense, we talk about architecture as a catalyst for: sustainable adaptation of the city’s infrastructure appropriate renovation of dilapidated urban districts strengthening of social cohesiveness in the city development...

  17. Microwave-assisted direct synthesis of butene from high-selectivity methane

    Science.gov (United States)

    Lu, Yi-heng; Li, Kang; Lu, Yu-wei

    2017-12-01

    Methane was directly converted to butene liquid fuel by microwave-induced non-oxidative catalytic dehydrogenation under 0.1-0.2 MPa. The results show that, under microwave heating in a two-stage fixed-bed reactor, in which nickel powder and NiOx-MoOy/SiO2 are used as the catalyst, the methane-hydrogen mixture is used as the raw material, with no acetylene detected. The methane conversion is more than 73.2%, and the selectivity of methane to butene is 99.0%. Increasing the hydrogen/methane feed volume ratio increases methane conversion and selectivity. Gas chromatography/electron impact ionization/mass spectrometry chromatographic analysis showed that the liquid fuel produced by methane dehydrogenation oligomerization contained 89.44% of butene, and the rest was acetic acid, ethanol, butenol and butyric acid, and the content was 1.0-3.0 wt%.

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

    KAUST Repository

    Takanabe, Kazuhiro

    2012-01-01

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

  19. Experimental study of methane partial oxidation on Ni-YSZ anode of solid oxide fuel cells

    Science.gov (United States)

    Iwai, Hiroshi; Tada, Koshi; Kishimoto, Masashi; Saito, Motohiro; Yoshida, Hideo

    2017-08-01

    The effects of oxygen addition to methane directly supplied to solid oxide fuel cells were investigated. Fundamental experiments were conducted using Ni-YSZ (yttria-stabilized zirconia) cermet as a typical anode material, and Ni-YSZ catalysts having different streamwise lengths were fabricated on YSZ flat plates. A premixed gas of methane, oxygen, nitrogen and steam was supplied to a test catalyst set in a rectangular test channel. The exhaust gas compositions and the surface temperature distributions of the test catalysts were measured. It was found that the oxidation of methane prominently proceeded near the upstream edge of the catalyst followed by steam/dry reforming reactions downstream. This resulted in the formation of a high-temperature region, leading to a large temperature gradient in the streamwise direction.

  20. Oscillatory Behavior during the Catalytic Partial Oxidation of Methane: Following Dynamic Structural Changes of Palladium Using the QEXAFS Technique

    DEFF Research Database (Denmark)

    Stoetzel, Jan; Frahm, Ronald; Kimmerle, Bertram

    2012-01-01

    as a combination of total oxidation and reforming in the catalytic capillary reactor was observed. This change in catalytic performance was directly linked to changes in the oxidation state of the Pd/Al2O3 catalysts at different positions along the catalytic reactor. During the ignition of the catalytic partial......Pd/Al2O3 catalysts oscillate between ignition and extinction of the catalytic partial oxidation of methane when they are exposed to a 2:1 reaction mixture of methane and oxygen. The oscillations of the catalytic performance and the structure of Pd/Al2O3 catalysts in a fixed-bed reactor were...... by the oven temperature than the ignition behavior of the catalytic partial oxidation of methane. This indicates that deactivation is caused by an autoreduction of the palladium at the beginning of the catalyst bed due to the high temperature achieved by total oxidation of methane....

  1. Alkali/TX{sub 2} catalysts for CO/H{sub 2} conversion to C{sub 1}-C{sub 4} alcohols. Technical progress report, March 1989--August 1989

    Energy Technology Data Exchange (ETDEWEB)

    Klier, K.; Herman, R.G.; Bastian, R.D.; Flanagan, K.L.

    1989-12-31

    Ruthenium disulfide catalysts have been synthesized, tested, and characterized during this period of research. It was observed that both the undoped and Cs-doped RuS{sub 2} catalysts produced alcohols and lower amounts of hydrocarbons from H{sub 2}/CO = 1.0 synthesis gas at temperatures above 300{degree}C. Calcination and catalytic testing resulted in partial reduction of the RuS{sub 2} to Ru{sup o}. Calcination under H{sub 2}S prevented the partial reduction of the RuS{sub 2} catalyst, but subsequent catalytic testing again resulted in the formation of a quantity of Ru{sup o}. A Cs-doped RuS{sub 2} catalyst was prepared, but it might have had too high of a loading of Cs. Upon testing, a lower activity was observed for the doped catalyst compared with the undoped catalyst, but the alcohol selectivity was the same for the two catalysts.

  2. Coal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kroenig, W.

    1944-02-11

    Some considerations in the selection of a catalyst for the liquid phase of coal hydrogenation are discussed. Some of the previous history of such selections is mentioned. At one stage of the development, the principal catalyst had been iron sulfate (FeSO/sub 4/.7H/sub 2/O). Later, for reasons of cost and availability of large supplies, selections had turned to mixtures of iron sulfate and one or another of some iron oxide- and aluminum oxide-containing byproducts of aluminum manufacture, namely Bayermasse, Luxamsse, or Lautamasse. Much of the discussion centered on optimal proportions for such mixtures, particularly as related to pH values of resulting coal pastes. Upper Silesian coal was more alkaline than Ruhr coal, and Bayermasse, etc., were quite alkaline. Thus, since the iron sulfate served as a partial neutralizer for the coal as well as a catalyst, it seemed necessary to increase the proportions of iron sulfate in the catalyst mixture when processing coal of greater alkalinity. A further reason for a greater proportion of iron sulfate seemed to be that most of the catalytic activity of the iron came from the ferrous iron of iron sulfate rather than from the ferric iron of the other materials. Ferrous-ferric ratios also seemed to indicate that Luxmasse or Lautamasse might be better catalyst components than Bayermasse but their water content sometimes caused handling problems, so Bayermasse had been more widely used. Formation of deposits in the preheater was more likely due to the Bayermasse than to the iron sulfate; sodium sulfide could help to prevent them.

  3. The direct aromatization of methane

    Energy Technology Data Exchange (ETDEWEB)

    Marcelin, G.; Oukaci, R.; Migone, R.A.; Kazi, A.M. [Altamira Instruments, Pittsburgh, PA (United States)

    1995-12-31

    The thermal decomposition of methane shows significant potential as a process for the production of higher unsaturated and aromatic hydrocarbons when the extent of the reaction is limited. Thermodynamic calculations have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that cooling the product and reacting gases as the reaction proceeds can significantly reduce or eliminate the formation of solid carbon and heavier (C{sub 10+}) materials. Much work remains to be done in optimizing the quenching process and this is one of the goals of this program. Means to lower the temperature of the reaction are being studied as this result in a more feasible commercial process due to savings realized in energy and material of construction costs. The use of free-radical generators and catalysts will be investigated as a means of lowering the reaction temperature thus allowing faster quenching. It is highly likely that such studies will lead to a successful direct methane to higher hydrocarbon process.

  4. Water effect in hydrogen production from methane

    Energy Technology Data Exchange (ETDEWEB)

    Acha, E.; Requies, J.; Barrio, V.L.; Cambra, J.F.; Gueemez, M.B.; Arias, P.L. [Chemical Engineering and Environmental Department, University of the Basque Country (UPV/EHU) 48013 Bilbao (Spain)

    2010-10-15

    Ni/MgO and Ni/Al{sub 2}O{sub 3} catalysts were prepared, by wet impregnation, to compare their performance in hydrogen production from methane CPO, wet-CPO and SR. The catalytic activity was tested at 1073 K, 1 bar and 600-1200 h{sup -1}. Fresh and used catalysts were characterized by different techniques. Both supports, as expected, had a low surface area (27.1 m{sup 2}/g MgO and 6.2 m{sup 2}/g {alpha}-Al{sub 2}O{sub 3}), as determined by BET method. The images obtained with SEM and TEM revealed that the Ni was more dispersed in the MgO support than in the Al{sub 2}O{sub 3} one. By XRD a strong interaction, as solid-solution, between NiO and MgO was found in the 30Ni/MgO and 40Ni/MgO catalysts. The fresh 40Ni/Al{sub 2}O{sub 3} reduced catalyst was partially reduced. But after the activity tests the stability of the reduced Ni became bigger. Some Ni sintering was also observed in the 40Ni/Al{sub 2}O{sub 3} after the wet-CPO and SR tests. The behaviour of the three catalysts was very good in CPO methane conversion (90-93%), but the gradual increase of the steam to carbon ratio, wet-CPO and SR, affected negatively the conversion. (author)

  5. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen.

    Science.gov (United States)

    Guo, Xiaoguang; Fang, Guangzong; Li, Gang; Ma, Hao; Fan, Hongjun; Yu, Liang; Ma, Chao; Wu, Xing; Deng, Dehui; Wei, Mingming; Tan, Dali; Si, Rui; Zhang, Shuo; Li, Jianqi; Sun, Litao; Tang, Zichao; Pan, Xiulian; Bao, Xinhe

    2014-05-09

    The efficient use of natural gas will require catalysts that can activate the first C-H bond of methane while suppressing complete dehydrogenation and avoiding overoxidation. We report that single iron sites embedded in a silica matrix enable direct, nonoxidative conversion of methane, exclusively to ethylene and aromatics. The reaction is initiated by catalytic generation of methyl radicals, followed by a series of gas-phase reactions. The absence of adjacent iron sites prevents catalytic C-C coupling, further oligomerization, and hence, coke deposition. At 1363 kelvin, methane conversion reached a maximum at 48.1% and ethylene selectivity peaked at 48.4%, whereas the total hydrocarbon selectivity exceeded 99%, representing an atom-economical transformation process of methane. The lattice-confined single iron sites delivered stable performance, with no deactivation observed during a 60-hour test.

  6. A generic model for photocatalytic activity as a function of catalyst thickness

    DEFF Research Database (Denmark)

    Nielsen, Morten G.; In, Su-Il; Vesborg, Peter C.K.

    2012-01-01

    value for increasing catalyst film thickness. Conversely, having opposing directions of illumination and incident gas, there exists an optimal catalyst film thickness with respect to activity. In the present work, we demonstrate, quantify and model this effect using methane photooxidation over PVD TiO2...

  7. Catalyst Architecture

    DEFF Research Database (Denmark)

    Catalyst Architecture’ takes its point of departure in a broadened understanding of the role of architecture in relation to developmental problems in large cities. Architectural projects frame particular functions and via their form language, they can provide the user with an aesthetic experience....... The broadened understanding of architecture consists in that an architectural project, by virtue of its placement in the context and of its composition of programs, can have a mediating role in a positive or cultural development of the district in question. In this sense, we talk about architecture as catalyst...... cities on the planet have growing pains and social cohesiveness is under pressure from an increased difference between rich and poor, social segregation, ghettoes, immigration of guest workers and refugees, commercial mass tourism etc. In this context, it is important to ask which role architecture...

  8. Immobilized triazacyclononane derivatives as selective oxidation catalysts. Final technical report of DOE Award No. DE-FG02-99ER14968 with the University of Munich [Encapsulation of metal chelate and oxocatalysts in nanoporous hosts

    Energy Technology Data Exchange (ETDEWEB)

    Bein, Thomas

    2002-10-28

    This project deals with the covalent anchoring of various derivatives of triazacyclononane (TACN)ligands in the channels of period mesoporous materials and the catalytic activity of the corresponding metal complexes. Catalyst preparation, ligand immobilization, catalyst characterization, and catalyst performance in selective oxidation are discussed. A wide range of pendant variations on the TACN ligand can be synthesized, and ligands can be covalently bound to high surface area, pseudo-crystalline, silicate solids, before or after pendant addition.

  9. Development of catalysts for chemical reactions driven by concentrated solar energy

    International Nuclear Information System (INIS)

    Berman, A.; Levitan, R.; Levy, M.

    1992-03-01

    The aim of this phase of the work is to study commercially available low priced catalysts, for the methanation and reforming processes in the closed-loop solar chemical heat pipe. This report summarized some long term tests of commercially available methanation catalysts and the measurement of their active surface before and after reaction. It was found that the 1%Ru on alumina stars catalysts (prepared by Englehard Company according to our request) is very active and stable at 350-750 C. The catalyst 'A' produced in Russia, is less active, however, did not lose the mechanical strength. The 50% Ni/SiO 2 catalyst is active as the 'A' catalyst but loses its activity after treatment at temperature > 600 C, its geometrical size shrinked. (authors). 25 refs., 25 figs., 36 tabs

  10. Low-Energy, Low-Cost Production of Ethylene by Low- Temperature Oxidative Coupling of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Radaelli, Guido [Siluria Technologies, Inc., San Francisco, CA (United States); Chachra, Gaurav [Siluria Technologies, Inc., San Francisco, CA (United States); Jonnavittula, Divya [Siluria Technologies, Inc., San Francisco, CA (United States)

    2017-12-30

    In this project, we develop a catalytic process technology for distributed small-scale production of ethylene by oxidative coupling of methane at low temperatures using an advanced catalyst. The Low Temperature Oxidative Coupling of Methane (LT-OCM) catalyst system is enabled by a novel chemical catalyst and process pioneered by Siluria, at private expense, over the last six years. Herein, we develop the LT-OCM catalyst system for distributed small-scale production of ethylene by identifying and addressing necessary process schemes, unit operations and process parameters that limit the economic viability and mass penetration of this technology to manufacture ethylene at small-scales. The output of this program is process concepts for small-scale LT-OCM catalyst based ethylene production, lab-scale verification of the novel unit operations adopted in the proposed concept, and an analysis to validate the feasibility of the proposed concepts.

  11. Doses from radioactive methane

    International Nuclear Information System (INIS)

    Phipps, A.W.; Kendall, G.M.; Fell, T.P.; Harrison, J.D.

    1990-01-01

    A possible radiation hazard arises from exposure to methane labelled with either a 3 H or a 14 C nuclide. This radioactive methane could be released from a variety of sources, e.g. land burial sites containing radioactive waste. Standard assumptions adopted for vapours would not apply to an inert alkane like methane. This paper discusses mechanisms by which radioactive methane would irradiate tissues and provides estimates of doses. Data on skin thickness and metabolism of methane are discussed with reference to these mechanisms. It is found that doses are dominated by dose from the small fraction of methane which is inhaled and metabolised. This component of dose has been calculated under rather conservative assumptions. (author)

  12. Advanced Heterogeneous Fenton Treatment of Coalbed Methane-Produced Water Containing Fracturing Fluid

    Directory of Open Access Journals (Sweden)

    Meng Zhang

    2018-04-01

    Full Text Available This study investigated the heterogeneous Fenton treatment to process coalbed methane-produced water containing fracturing fluid and chose the development region of coalbed methane in the Southern Qinshui Basin as a research area. We synthesized the catalyst of Fe-Co/γ-Al2O3 by homogeneous precipitation method and characterized it by BET, XRD, SEM-EDS, FTIR, and XPS. Based on the degradation rate, we studied the influences of the heterogeneous Fenton method on the coalbed methane output water treatment process parameters, including initial pH, H2O2 concentration, and the catalyst concentration. We also investigated the impacts of overall reaction kinetics of heterogeneous catalytic oxidation on coalbed methane-produced water containing fracturing fluid. Results showed that Fe-Co/γ-Al2O3 as a Fenton catalyst has a good catalytic oxidation effect and can effectively process coalbed methane-produced water. This reaction also followed first-order kinetics. The optimal conditions were as follows: the initial pH of 3.5, a H2O2 concentration of 40 mol L−1, a catalyst concentration of 4 g/L, and an apparent reaction rate constant of 0.0172 min−1. Our results provided a basis to establish methods for treating coalbed methane-produced water.

  13. Evidence of Scrambling over Ruthenium-based Catalysts in Supercritical-water Gasification

    DEFF Research Database (Denmark)

    Peterson, Andrew A.; Dreher, Marian; Wambach, Jörg

    2012-01-01

    Catalytic processes that employ Ru catalysts in supercritical water have been shown to be capable of converting organics, such as wood waste, into synthetic natural gas (CH4) with high efficiencies at relatively moderate temperatures of around 400°C. However, the exact roles of the catalyst and t...... that a characteristic of an effective catalyst for supercritical water gasification to methane is its ability to promote rapid equilibria through scrambling mechanisms....

  14. Use of ionic liquids as coordination ligands for organometallic catalysts

    Science.gov (United States)

    Li, Zaiwei [Moreno Valley, CA; Tang, Yongchun [Walnut, CA; Cheng,; Jihong, [Arcadia, CA

    2009-11-10

    Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

  15. Methanation process utilizing split cold gas recycle

    Science.gov (United States)

    Tajbl, Daniel G.; Lee, Bernard S.; Schora, Jr., Frank C.; Lam, Henry W.

    1976-07-06

    In the methanation of feed gas comprising carbon monoxide and hydrogen in multiple stages, the feed gas, cold recycle gas and hot product gas is mixed in such proportions that the mixture is at a temperature sufficiently high to avoid carbonyl formation and to initiate the reaction and, so that upon complete reaction of the carbon monoxide and hydrogen, an excessive adiabatic temperature will not be reached. Catalyst damage by high or low temperatures is thereby avoided with a process that utilizes extraordinarily low recycle ratios and a minimum of investment in operating costs.

  16. Homogeneous catalyst formulations for methanol production

    Science.gov (United States)

    Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

    1990-01-01

    There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

  17. Wide area methane emissions mapping with airborne IPDA lidar

    Science.gov (United States)

    Bartholomew, Jarett; Lyman, Philip; Weimer, Carl; Tandy, William

    2017-08-01

    Methane emissions from natural gas production, storage, and transportation are potential sources of greenhouse gas emissions. Methane leaks also constitute revenue loss potential from operations. Since 2013, Ball Aerospace has been developing advanced airborne sensors using integrated path differential absorption (IPDA) LIDAR instrumentation to identify methane, propane, and longer-chain alkanes in the lowest region of the atmosphere. Additional funding has come from the U.S. Department of Transportation, Pipeline and Hazardous Materials Administration (PHMSA) to upgrade instrumentation to a broader swath coverage of up to 400 meters while maintaining high spatial sampling resolution and geolocation accuracy. Wide area coverage allows efficient mapping of emissions from gathering and distribution networks, processing facilities, landfills, natural seeps, and other distributed methane sources. This paper summarizes the benefits of advanced instrumentation for aerial methane emission mapping, describes the operating characteristics and design of this upgraded IPDA instrumentation, and reviews technical challenges encountered during development and deployment.

  18. Methane Hydrate Field Program. Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

    Energy Technology Data Exchange (ETDEWEB)

    Collett, Tim [U.S. Geological Survey, Boulder, CO (United States); Bahk, Jang-Jun [Korea Inst. of Geoscience and Mineral Resources, Daejeon (Korea); Frye, Matt [U.S. Bureau of Ocean Energy Management, Sterling, VA (United States); Goldberg, Dave [Lamont-Doherty Earth Observatory, Palisades, NY (United States); Husebo, Jarle [Statoil ASA, Stavenger (Norway); Koh, Carolyn [Colorado School of Mines, Golden, CO (United States); Malone, Mitch [Texas A & M Univ., College Station, TX (United States); Shipp, Craig [Shell International Exploration and Production Inc., Anchorage, AK (United States); Torres, Marta [Oregon State Univ., Corvallis, OR (United States); Myers, Greg [Consortium For Ocean Leadership Inc., Washington, DC (United States); Divins, David [Consortium For Ocean Leadership Inc., Washington, DC (United States); Morell, Margo [Consortium For Ocean Leadership Inc., Washington, DC (United States)

    2013-12-31

    This topical report represents a pathway toward better understanding of the impact of marine methane hydrates on safety and seafloor stability and future collection of data that can be used by scientists, engineers, managers and planners to study climate change and to assess the feasibility of marine methane hydrate as a potential future energy resource. Our understanding of the occurrence, distribution and characteristics of marine methane hydrates is incomplete; therefore, research must continue to expand if methane hydrates are to be used as a future energy source. Exploring basins with methane hydrates has been occurring for over 30 years, but these efforts have been episodic in nature. To further our understanding, these efforts must be more regular and employ new techniques to capture more data. This plan identifies incomplete areas of methane hydrate research and offers solutions by systematically reviewing known methane hydrate “Science Challenges” and linking them with “Technical Challenges” and potential field program locations.

  19. Selective Coke Combustion by Oxygen Pulsing During Mo/ZSM‐5‐Catalyzed Methane Dehydroaromatization

    Science.gov (United States)

    Coumans, Ferdy J. A. G.; Uslamin, Evgeny; Kapteijn, Freek

    2016-01-01

    Abstract Non‐oxidative methane dehydroaromatization is a promising reaction to directly convert natural gas into aromatic hydrocarbons and hydrogen. Commercialization of this technology is hampered by rapid catalyst deactivation because of coking. A novel approach is presented involving selective oxidation of coke during methane dehydroaromatization at 700 °C. Periodic pulsing of oxygen into the methane feed results in substantially higher cumulative product yield with synthesis gas; a H2/CO ratio close to two is the main side‐product of coke combustion. Using 13C isotope labeling of methane it is demonstrated that oxygen predominantly reacts with molybdenum carbide species. The resulting molybdenum oxides catalyze coke oxidation. Less than one‐fifth of the available oxygen reacts with gaseous methane. Combined with periodic regeneration at 550 °C, this strategy is a significant step forward, towards a process for converting methane into liquid hydrocarbons. PMID:27791321

  20. Ammonia treated Mo/AC catalysts for CO hydrogenation with ...

    Indian Academy of Sciences (India)

    SHARIF F ZAMAN

    K-Ni-Mo catalyst. The interaction of activated carbon with the Ni-Mo species prevents the complete reduc- tion of the active metals (Ni0 and Mo0 lead to methane formation) and preserves partially oxidized Mo and Ni species, which are thought to be active sites for alcohol formation.14 Zhang et al.,15 synthesized Ni-Mo-K ...

  1. Methane formation from the hydrogenation of carbon dioxide on Ni(110) surface--a density functional theoretical study.

    Science.gov (United States)

    Bothra, Pallavi; Periyasamy, Ganga; Pati, Swapan K

    2013-04-21

    The complete hydrogenation mechanisms of CO2 are explored on Ni(110) surface catalyst using density functional theory. We have studied the possible hydrogenation mechanism to form product methane from the stable adsorption-co-adsorption intermediates of CO2 and H2 on Ni(110) surface. Our computations clearly elucidate that the mechanism for the formation of methyl, methoxy and methane moieties from carbon dioxide on the nickel catalyst. Moreover, our studies clearly show that the methane formation via hydroxyl carbonyl intermediate requires a lower energy barrier than via carbon monoxide and formate intermediates on the Ni(110) surface.

  2. An introduction to catalyst

    International Nuclear Information System (INIS)

    Jeon, Hak Je

    1988-11-01

    This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

  3. Minimizing methane release

    NARCIS (Netherlands)

    Arendonk, van J.A.M.

    2014-01-01

    "Methane emissions from cows are decreasing, but not at the pace which the agricultural sector and the government agreed. The project, Reduced methane emission of dairy cows (ME001), will provide insights that enable targeted interventions for a 30% reduction of greenhouse gasses in the Netherlands

  4. Methane and Climate Change

    NARCIS (Netherlands)

    Reay, D.; Smith, P.; Amstel, van A.R.

    2010-01-01

    Methane is a powerful greenhouse gas and is estimated to be responsible for approximately one-fifth of man-made global warming. Per kilogram, it is 25 times more powerful than carbon dioxide over a 100-year time horizon -- and global warming is likely to enhance methane release from a number of

  5. Utilization of coalbed methane

    Energy Technology Data Exchange (ETDEWEB)

    Gustavson, J.B. [Gustavson Associates Inc., Boulder, CO (United States)

    1996-02-01

    Substantial progress has been made in capturing coalbed methane (CBM gas), which constitutes a valuable source of clean burning energy. It is of importance to study the various potential uses of coalbed methane and to understand the various technologies required, as well as their economics and any institutional constraints. In industrialised countries, the uses of coalbed methane are almost solely dependent on microeconomics; coalbed methane must compete for a market against natural gas and other energy sources - and frequently, coalbed methane is not competitive against other energy sources. In developing countries, on the other hand, particularly where other sources of energy are in short supply, coalbed methane economics yield positive results. Here, constraints to development of CBM utilization are mainly lack of technology and investment capital. Sociological aspects such as attitude and cultural habits, may also have a strong negative influence. This paper outlines the economics of coalbed methane utilization, particularly its competition with natural gas, and touches upon the many different uses to which coalbed methane may be applied. 24 refs., 4 figs.

  6. Guide of good practices for methanization projects

    International Nuclear Information System (INIS)

    Delatte, Constant; Orozco-Souel, Paola; Rouxel, Anaick; Tanneau, Patrick; Schreiber, Konrad; Jaubert, Jean Noel; Micone, Philippe; Dionne, Denis; Renner, Christophe; Ollivier, Denis

    2011-12-01

    This guide aims at providing project holders with guidance on factors which may influence social acceptability of methanization projects and with recommendations regarding communication and dialogue for a better project integration, with a technical support in order to guarantee project quality for a minimised environmental impact, and at convincing and reassuring local communities which plan to implement a methanization project, notably with respect to issues like odours, safety or landscape integration. The guide first outlines the importance of a serious and credible approach, and aims project holders at demonstrating an actual reasonable economic control of energy, environmental and social issues related to their project. The second part proposes technical solutions regarding the limitation of impact on air quality, preservation and restoration of soil quality and water resources, landscape integration, transport management and noise prevention. Feedbacks on experiences with different types of installations (agricultural, industrial, and so on) are also provided. A good practice charter is finally proposed

  7. Exploiting coalbed methane and protecting the global environment

    Energy Technology Data Exchange (ETDEWEB)

    Yuheng, Gao

    1996-12-31

    The global climate change caused by greenhouse gases (GHGs) emission has received wide attention from all countries in the world. Global environmental protection as a common problem has confronted the human being. As a main component of coalbed methane, methane is an important factor influencing the production safety of coal mine and threatens the lives of miners. The recent research on environment science shows that methane is a very harmful GHG. Although methane gas has very little proportion in the GHGs emission and its stayed period is also very short, it has very obvious impact on the climate change. From the estimation, methane emission in the coal-mining process is only 10% of the total emission from human`s activities. As a clean energy, Methane has mature recovery technique before, during and after the process of mining. Thus, coalbed methane is the sole GHG generated in the human`s activities and being possible to be reclaimed and utilized. Compared with the global greenhouse effect of other GHGs emission abatement, coalbed methane emission abatement can be done in very low cost with many other benefits: (1) to protect global environment; (2) to improve obviously the safety of coal mine; and (3) to obtain a new kind of clean energy. Coal is the main energy in China, and coalbed contains very rich methane. According to the exploration result in recent years, about 30000{approximately}35000 billion m{sup 2} methane is contained in the coalbed below 2000 m in depth. China has formed a good development base in the field of reclamation and utilization of coalbed methane. The author hopes that wider international technical exchange and cooperation in the field will be carried out.

  8. Catalyst Schools Research Study: Technical Report

    Science.gov (United States)

    Hammer, Patricia Cahape

    2016-01-01

    In January 2012, the West Virginia Governor's Office released an influential report, "Education Efficiency Audit of West Virginia's Primary and Secondary Education System," written by Public Works (2012), a management consulting company headquartered in West Chester, Pennsylvania. Based largely on this report, the West Virginia…

  9. Methane Emission by Camelids

    Science.gov (United States)

    Dittmann, Marie T.; Runge, Ullrich; Lang, Richard A.; Moser, Dario; Galeffi, Cordula; Kreuzer, Michael; Clauss, Marcus

    2014-01-01

    Methane emissions from ruminant livestock have been intensively studied in order to reduce contribution to the greenhouse effect. Ruminants were found to produce more enteric methane than other mammalian herbivores. As camelids share some features of their digestive anatomy and physiology with ruminants, it has been proposed that they produce similar amounts of methane per unit of body mass. This is of special relevance for countrywide greenhouse gas budgets of countries that harbor large populations of camelids like Australia. However, hardly any quantitative methane emission measurements have been performed in camelids. In order to fill this gap, we carried out respiration chamber measurements with three camelid species (Vicugna pacos, Lama glama, Camelus bactrianus; n = 16 in total), all kept on a diet consisting of food produced from alfalfa only. The camelids produced less methane expressed on the basis of body mass (0.32±0.11 L kg−1 d−1) when compared to literature data on domestic ruminants fed on roughage diets (0.58±0.16 L kg−1 d−1). However, there was no significant difference between the two suborders when methane emission was expressed on the basis of digestible neutral detergent fiber intake (92.7±33.9 L kg−1 in camelids vs. 86.2±12.1 L kg−1 in ruminants). This implies that the pathways of methanogenesis forming part of the microbial digestion of fiber in the foregut are similar between the groups, and that the lower methane emission of camelids can be explained by their generally lower relative food intake. Our results suggest that the methane emission of Australia's feral camels corresponds only to 1 to 2% of the methane amount produced by the countries' domestic ruminants and that calculations of greenhouse gas budgets of countries with large camelid populations based on equations developed for ruminants are generally overestimating the actual levels. PMID:24718604

  10. Methane emission by camelids.

    Directory of Open Access Journals (Sweden)

    Marie T Dittmann

    Full Text Available Methane emissions from ruminant livestock have been intensively studied in order to reduce contribution to the greenhouse effect. Ruminants were found to produce more enteric methane than other mammalian herbivores. As camelids share some features of their digestive anatomy and physiology with ruminants, it has been proposed that they produce similar amounts of methane per unit of body mass. This is of special relevance for countrywide greenhouse gas budgets of countries that harbor large populations of camelids like Australia. However, hardly any quantitative methane emission measurements have been performed in camelids. In order to fill this gap, we carried out respiration chamber measurements with three camelid species (Vicugna pacos, Lama glama, Camelus bactrianus; n = 16 in total, all kept on a diet consisting of food produced from alfalfa only. The camelids produced less methane expressed on the basis of body mass (0.32±0.11 L kg⁻¹ d⁻¹ when compared to literature data on domestic ruminants fed on roughage diets (0.58±0.16 L kg⁻¹ d⁻¹. However, there was no significant difference between the two suborders when methane emission was expressed on the basis of digestible neutral detergent fiber intake (92.7±33.9 L kg⁻¹ in camelids vs. 86.2±12.1 L kg⁻¹ in ruminants. This implies that the pathways of methanogenesis forming part of the microbial digestion of fiber in the foregut are similar between the groups, and that the lower methane emission of camelids can be explained by their generally lower relative food intake. Our results suggest that the methane emission of Australia's feral camels corresponds only to 1 to 2% of the methane amount produced by the countries' domestic ruminants and that calculations of greenhouse gas budgets of countries with large camelid populations based on equations developed for ruminants are generally overestimating the actual levels.

  11. Methane emission by camelids.

    Science.gov (United States)

    Dittmann, Marie T; Runge, Ullrich; Lang, Richard A; Moser, Dario; Galeffi, Cordula; Kreuzer, Michael; Clauss, Marcus

    2014-01-01

    Methane emissions from ruminant livestock have been intensively studied in order to reduce contribution to the greenhouse effect. Ruminants were found to produce more enteric methane than other mammalian herbivores. As camelids share some features of their digestive anatomy and physiology with ruminants, it has been proposed that they produce similar amounts of methane per unit of body mass. This is of special relevance for countrywide greenhouse gas budgets of countries that harbor large populations of camelids like Australia. However, hardly any quantitative methane emission measurements have been performed in camelids. In order to fill this gap, we carried out respiration chamber measurements with three camelid species (Vicugna pacos, Lama glama, Camelus bactrianus; n = 16 in total), all kept on a diet consisting of food produced from alfalfa only. The camelids produced less methane expressed on the basis of body mass (0.32±0.11 L kg⁻¹ d⁻¹) when compared to literature data on domestic ruminants fed on roughage diets (0.58±0.16 L kg⁻¹ d⁻¹). However, there was no significant difference between the two suborders when methane emission was expressed on the basis of digestible neutral detergent fiber intake (92.7±33.9 L kg⁻¹ in camelids vs. 86.2±12.1 L kg⁻¹ in ruminants). This implies that the pathways of methanogenesis forming part of the microbial digestion of fiber in the foregut are similar between the groups, and that the lower methane emission of camelids can be explained by their generally lower relative food intake. Our results suggest that the methane emission of Australia's feral camels corresponds only to 1 to 2% of the methane amount produced by the countries' domestic ruminants and that calculations of greenhouse gas budgets of countries with large camelid populations based on equations developed for ruminants are generally overestimating the actual levels.

  12. Nitrogen-doped carbon nanotubes as a metal catalyst support

    CSIR Research Space (South Africa)

    Mabena, LF

    2011-05-01

    Full Text Available The science and technology of catalysis is of fundamental importance to a national economy. Today about 90% of all technical chemicals are manufactured by the use of catalysts. Nanoparticles of noble metals are extremely important materials...

  13. Methane oxidation with low O2/CH4 ratios in the present of water: Combustion or reforming

    International Nuclear Information System (INIS)

    Geng, Haojie; Yang, Zhongqing; Zhang, Li; Ran, Jingyu; Yan, Yunfei

    2017-01-01

    Highlights: • Copper catalyst displays an inhibitory effect of water while cobalt catalyst does not. • Both catalysts show their catalytic ability for oxidation and reforming reaction. • Oxidation precedes reforming in methane reaction over both catalysts. • Water participates in reforming reaction and shows increasing effect in high temperature. - Abstract: This paper investigates the reaction of methane over copper and cobalt catalysts under oxygen-deficient conditions with added water. A fixed-bed reactor, TPD analysis, in situ DRIFTS study, and temperature detection were used to test the activity of the methane reaction, water adsorption on the metal surface, OH group behavior, and the endothermic and exothermic processes of the reaction. The results show that the inhibitory effect of water mainly occurs at a low temperature and methane conversion decreases when water is introduced into the feed. Water easily adsorbs on metal clusters and forms OH groups at low temperatures. Copper tends to adsorb more water than cobalt and shows a stronger inhibitory effect. The DRIFTS spectra of the Cu catalyst show strong OH peaks during the reaction, of which the magnitudes increase with the water pressure. When the reaction temperature rises (750 °C), water begins to serve as an oxidant and participates in the reforming reaction. Both catalysts show a transition process between the oxidation and reforming reactions as the temperature increases. Co displays a better catalytic performance in the reforming reaction. Oxidation precedes reforming; water does not participate in the reaction if the oxygen is not fully consumed.

  14. Hydrogenation of Carbon Dioxide to Methane by Ruthenium Nanoparticles in Ionic Liquid.

    Science.gov (United States)

    Melo, Catarina I; Szczepańska, Anna; Bogel-Łukasik, Ewa; Nunes da Ponte, Manuel; Branco, Luís C

    2016-05-23

    The efficient transformation of carbon dioxide into fuels can be an excellent alternative to sequestration. In this work, we describe CO2 hydrogenation to methane in imidazolium-based ionic liquid media, using ruthenium nanoparticles prepared in situ as catalyst. The best yield of methane (69 %) was achieved using 0.24 mol % ruthenium catalyst (in [omim][NTf2 ], 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide, at 40 bar of hydrogen pressure plus 40 bar of CO2 pressure, and at 150 °C. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Oscillatory behaviour of catalytic properties, structure and temperature during the catalytic partial oxidation of methane on Pd/Al2O3

    DEFF Research Database (Denmark)

    Kimmerle, B.; Baiker, A.; Grunwaldt, Jan-Dierk

    2010-01-01

    Pd/Al2O3 catalysts showed an oscillatory behaviour during the catalytic partial oxidation (CPO) of methane, which was investigated simultaneously by IR-thermography, X-ray absorption spectroscopy, and online mass-spectrometry to correlate the temperature, state of the catalyst and catalytic...... to self-reduction leading to extinction of the process. The latter was the key driver for the oscillations and thus gave additional insight into the mechanism of partial methane oxidation....

  16. Revival of Archaeal Methane Microbiology.

    Science.gov (United States)

    Welte, Cornelia U

    2018-01-01

    The methane concentration in the Earth's atmosphere is rising, and, as methane is a potent greenhouse gas, it contributes considerably to climate change. It is produced by methanogenic archaea that thrive in anoxic habitats and can be oxidized by methane-oxidizing bacteria or archaea. In this Perspective , recent innovations and discoveries in archaeal methane microbiology are discussed and a future outlook on how novel methane-metabolizing archaea might be cultivated is provided.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-22

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

  18. Methane prediction in collieries

    CSIR Research Space (South Africa)

    Creedy, DP

    1999-06-01

    Full Text Available The primary aim of the project was to assess the current status of research on methane emission prediction for collieries in South Africa in comparison with methods used and advances achieved elsewhere in the world....

  19. Methane monitoring from space

    Science.gov (United States)

    Stephan, C.; Alpers, M.; Millet, B.; Ehret, G.; Flamant, P.

    2017-11-01

    Methane is one of the strongest anthropogenic greenhouse gases. It contributes by its radiative forcing significantly to the global warming. For a better understanding of climate changes, it is necessary to apply precise space-based measurement techniques in order to obtain a global view on the complex processes that control the methane concentration in the atmosphere. The MERLIN mission is a joint French-German cooperation, on a micro satellite mission for space-based measurement of spatial and temporal gradients of atmospheric methane columns on a global scale. MERLIN will be the first Integrated Path Differential Absorption LIDAR for greenhouse gas monitoring from space. In contrast to passive methane missions, the LIDAR instrument allows measurements at alllatitudes, all-seasons and during night.

  20. Potential for CO2 sequestration and enhanced coalbed methane production in the Netherlands

    NARCIS (Netherlands)

    Hamelinck, C.N.; Schreurs, H.; Faaij, A.P.C.; Ruijg, G.J.; Jansen, Daan; Pagnier, H.; Bergen, F. van; Wolf, K.-H.; Barzandji, O.; Bruining, H.

    2006-01-01

    This study investigated the technical and economic feasibility of using CO2 for the enhanced production of coal bed methane (ECBM) in the Netherlands. This concept could lead to both CO2 storage by adsorbing CO2 in deep coal layers that are not suitable for mining, as well as production of methane.

  1. Terrestrial plant methane production

    DEFF Research Database (Denmark)

    Mikkelsen, Teis Nørgaard; Bruhn, Dan; Møller, Ian M.

    We evaluate all experimental work published on the phenomenon of aerobic methane (CH4) generation in terrestrial plants. We conclude that the phenomenon is true. Four stimulating factors have been observed to induce aerobic plant CH4 production, i.e. cutting injuries, increasing temperature...... the aerobic methane emission in plants. Future work is needed for establishing the relative contribution of several proven potential CH4 precursors in plant material....

  2. Oxidative coupling of methane using inorganic membrane reactor

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Y.H.; Moser, W.R.; Dixon, A.G. [Worcester Polytechnic Institute, MA (United States)] [and others

    1995-12-31

    The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.

  3. Catalytic reforming of methane to syngas in an oxygen-permeative membrane reactor

    Science.gov (United States)

    Urano, Takeshi; Kubo, Keiko; Saito, Tomoyuki; Hitomi, Atsushi

    2011-05-01

    For fuel cell applications, partial oxidative reforming of methane to syngas, hydrogen and carbon monoxide, was performed via a dense oxygen-permeative ceramic membrane composed by both ionic and electronic conductive materials. The modification of Ni-based catalyst by noble metals was investigated to increase oxygen permeation flux and decrease carbon deposition during reforming reaction. The role of each component in catalyst was also discussed.

  4. Oxidation catalysts comprising metal exchanged hexaaluminate wherein the metal is Sr, Pd, La, and/or Mn

    Science.gov (United States)

    Wickham, David [Boulder, CO; Cook, Ronald [Lakewood, CO

    2008-10-28

    The present invention provides metal-exchanged hexaaluminate catalysts that exhibit good catalytic activity and/or stability at high temperatures for extended periods with retention of activity as combustion catalysts, and more generally as oxidation catalysts, that make them eminently suitable for use in methane combustion, particularly for use in natural gas fired gas turbines. The hexaaluminate catalysts of this invention are of particular interest for methane combustion processes for minimization of the generation of undesired levels (less than about 10 ppm) of NOx species. Metal exchanged hexaaluminate oxidation catalysts are also useful for oxidation of volatile organic compounds (VOC), particularly hydrocarbons. Metal exchanged hexaaluminate oxidation catalysts are further useful for partial oxidation, particularly at high temperatures, of reduced species, particularly hydrocarbons (alkanes and alkenes).

  5. Methane Hydrate Field Program: Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

    Energy Technology Data Exchange (ETDEWEB)

    Myers, Greg [Consortium for Ocean Leadership, Washington, DC (United States)

    2014-02-01

    This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report: Historical Methane Hydrate Project Review Report; Methane Hydrate Workshop Report; Topical Report: Marine Methane Hydrate Field Research Plan; and Final Scientific/Technical Report.

  6. Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

    Energy Technology Data Exchange (ETDEWEB)

    Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan, E-mail: doan.phamminh@mines-albi.fr

    2016-12-30

    Highlights: • Formation of nanoparticles of Pt and Ru on hydroxyapatite surface support (HAP). • Pt catalyst more active and stable than Ru catalyst in dry reforming of methane (DRM). • Low carbon deposition on the surface of Pt catalyst after reaction. • Quantification of water as by-product of the reaction for the first time. • Good mass balance of the reaction. - Abstract: This work focused on the catalytic transformation of methane (CH{sub 4}) and carbon dioxide (CO{sub 2}) into syngas (mixture of CO and H{sub 2}). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400–700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

  7. Oxidation of methane by a biological dicopper centre.

    Science.gov (United States)

    Balasubramanian, Ramakrishnan; Smith, Stephen M; Rawat, Swati; Yatsunyk, Liliya A; Stemmler, Timothy L; Rosenzweig, Amy C

    2010-05-06

    Vast world reserves of methane gas are underutilized as a feedstock for the production of liquid fuels and chemicals owing to the lack of economical and sustainable strategies for the selective oxidation of methane to methanol. Current processes to activate the strong C-H bond (104 kcal mol(-1)) in methane require high temperatures, are costly and inefficient, and produce waste. In nature, methanotrophic bacteria perform this reaction under ambient conditions using metalloenzymes called methane monooxygenases (MMOs). MMOs thus provide the optimal model for an efficient, environmentally sound catalyst. There are two types of MMO. Soluble MMO (sMMO) is expressed by several strains of methanotroph under copper-limited conditions and oxidizes methane with a well-characterized catalytic di-iron centre. Particulate MMO (pMMO) is an integral membrane metalloenzyme produced by all methanotrophs and is composed of three subunits, pmoA, pmoB and pmoC, arranged in a trimeric alpha(3)beta(3)gamma(3) complex. Despite 20 years of research and the availability of two crystal structures, the metal composition and location of the pMMO metal active site are not known. Here we show that pMMO activity is dependent on copper, not iron, and that the copper active site is located in the soluble domains of the pmoB subunit rather than within the membrane. Recombinant soluble fragments of pmoB (spmoB) bind copper and have propylene and methane oxidation activities. Disruption of each copper centre in spmoB by mutagenesis indicates that the active site is a dicopper centre. These findings help resolve the pMMO controversy and provide a promising new approach to developing environmentally friendly C-H oxidation catalysts.

  8. Steam reforming of technical bioethanol for hydrogen production

    DEFF Research Database (Denmark)

    Rass-Hansen, Jeppe; Johansson, Roger; Møller, Martin Hulbek

    2008-01-01

    distillation fractions of technical 2nd generation bioethanol, produced in a pilot plant, influence the performance of nickel- and ruthenium-based catalysts during steam reforming, and we discuss what is required to obtain high activity and long catalyst lifetime. We conclude that the use of technical...

  9. Steam Methane Reformation Testing for Air-Independent Solid Oxide Fuel Cell Systems

    Science.gov (United States)

    Mwara, Kamwana N.

    2015-01-01

    Recently, NASA has been looking into utilizing landers that can be propelled by LOX-CH (sub 4), to be used for long duration missions. Using landers that utilize such propellants, also provides the opportunity to use solid oxide fuel cells as a power option, especially since they are able to process methane into a reactant through fuel reformation. One type of reformation, called steam methane reformation, is a process to reform methane into a hydrogen-rich product by reacting methane and steam (fuel cell exhaust) over a catalyst. A steam methane reformation system could potentially use the fuel cell's own exhaust to create a reactant stream that is hydrogen-rich, and requires less internal reforming of the incoming methane. Also, steam reformation may hold some advantages over other types of reforming, such as partial oxidation (PROX) reformation. Steam reformation does not require oxygen, while up to 25 percent can be lost in PROX reformation due to unusable CO (sub 2) reformation. NASA's Johnson Space Center has conducted various phases of steam methane reformation testing, as a viable solution for in-space reformation. This has included using two different types of catalysts, developing a custom reformer, and optimizing the test system to find the optimal performance parameters and operating conditions.

  10. A Review of the Methane Hydrate Program in Japan

    Directory of Open Access Journals (Sweden)

    Ai Oyama

    2017-09-01

    Full Text Available In this paper, methane hydrate R&D in Japan was examined in the context of Japan’s evolving energy policies. Methane hydrates have been studied extensively in Japanese national R&D programs since 1993, with the goal of utilizing them as an energy resource. Currently, the Research Consortium for Methane Hydrate Resources in Japan (MH 21 is in the third phase of a project that began in early 2002. Based on publicly available reports and other publications, and presentations made at the ten International Workshops for Methane Hydrate Research and Development, we have attempted to provide a timeline and a succinct summary of the major technical accomplishments of MH 21 during project Phases 1, 2, and 3.

  11. Hydrogen production from methane using oxygen-permeable ceramic membranes

    Science.gov (United States)

    Faraji, Sedigheh

    Non-porous ceramic membranes with mixed ionic and electronic conductivity have received significant interest in membrane reactor systems for the conversion of methane and higher hydrocarbons to higher value products like hydrogen. However, hydrogen generation by this method has not yet been commercialized and suffers from low membrane stability, low membrane oxygen flux, high membrane fabrication costs, and high reaction temperature requirements. In this dissertation, hydrogen production from methane on two different types of ceramic membranes (dense SFC and BSCF) has been investigated. The focus of this research was on the effects of different parameters to improve hydrogen production in a membrane reactor. These parameters included operating temperature, type of catalyst, membrane material, membrane thickness, membrane preparation pH, and feed ratio. The role of the membrane in the conversion of methane and the interaction with a Pt/CeZrO2 catalyst has been studied. Pulse studies of reactants and products over physical mixtures of crushed membrane material and catalyst have clearly demonstrated that a synergy exists between the membrane and the catalyst under reaction conditions. The degree of catalyst/membrane interaction strongly impacts the conversion of methane and the catalyst performance. During thermogravimetric analysis, the onset temperature of oxygen release for BSCF was observed to be lower than that for SFC while the amount of oxygen release was significantly greater. Pulse injections of CO2 over crushed membranes at 800°C have shown more CO2 dissociation on the BSCF membrane than the SFC membrane, resulting in higher CO formation on the BSCF membrane. Similar to the CO2 pulses, when CO was injected on the samples at 800°C, CO2 production was higher on BSCF than SFC. It was found that hydrogen consumption on BSCF particles is 24 times higher than that on SFC particles. Furthermore, Raman spectroscopy and temperature programmed desorption studies of

  12. C-13 isotopic studies of the surface catalysed reactions of methane

    International Nuclear Information System (INIS)

    Long, M.A.; He, S.J.X.; Adebajo, M.

    1997-01-01

    The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

  13. Factors affecting the catalytic oligomerization of methane via microwave heating

    Science.gov (United States)

    Conde, Luis Daniel

    Catalytic microwave heating has been used as a method for the oligomerization of methane to higher hydrocarbons. Many catalysts were tested in this reaction. Nickel powder, raney nickel, iron powder and activated carbon were the most active and efficient catalysts for the production of higher hydrocarbons. When helium was used as a diluent gas and the applied power was optimized, the selectivities were controlled to the most desired products. In general, the most abundant products for all the experiments were C2s. Iron powder was active only at high power (1130 W). At these conditions acetylene was avoided and ethylene and ethane were produced in the same proportion. Activated carbon catalysts with helium as diluent led to a selectivity towards benzene up to 33%. Some manganese oxides such as OMS-1, OMS-2 and MnO2 (dielectric constant, epsilon ≈ 104) were not active in these reactions. These data suggest that the dielectric constant is not the most important factor in the oligomerization of methane via microwave heating. Conversion and activities of these materials are not proportionally related to the surface area of the catalysts. Higher catalytic activity was observed for Raney nickel than for regular nickel powder. The maximum conversion obtained was 24% at 400 W and 10 min of irradiation time. For regular nickel powder that conversion can be achieved only after 700 W of power and more than 20 min of reaction. BET surface area, Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy, and Temperature-Programmed Desorption and Reduction analysis were performed to characterize the catalyst before and after reaction. Deactivation of Raney nickel by fouling and sintering was observed after 500 W and/or 15 min of reaction. The effect of microwave radiation frequency on activity and product distribution for methane oligomerization has been studied. Nickel, iron, and activated carbon catalysts were used in these studies. Experiments were done with pure methane

  14. Methanation of carbon oxides. History, status quo and future perspectives

    Energy Technology Data Exchange (ETDEWEB)

    Kaltner, W.; Rakoczy, R.A. [Clariant SE, Muenchen (Germany)

    2012-07-01

    With increasing demand in fossil sources and especially crude oil based energy carrier, proven reserves will be diminishing. Besides alternative and sustainable sources the conversion of coal into fuels which can be distributed within the existing infrastructure becomes extremely important in areas of fast growing energy demand. Driver for these technologies is mostly the lack of crude oil and availability of coal like in China or South Africa. The most common way to convert coal into chemicals and fuels is the gasification to yield a gas mixture known as synthesis gas. Synthesis gas can be converted in highly pure methane used as 'substitute natural gas' (SNG) in gas grids of major cities to produce heat at home and industry. All available SNG technologies are characterized by the difficulty to control the extreme heat release of the methanation reaction. This presentation will give an overview on available gasification and methanation technologies from recent point of view. A lot of processes are already described in literature and there are pilot and real plants for methanation and especially SNG built. Moreover, a new process to produce methane from synthesis gas without the need of recycle streams and high temperatures will be introduced. This novel process developed by Foster Wheeler - using catalysts from Clariant - is called 'VESTA Process' in accordance with the Roman goddess of hearth and fire. (orig.)

  15. Feasibility of ethylene synthesis via oxidative coupling of methane

    International Nuclear Information System (INIS)

    Bhasin, M.M.

    1988-01-01

    Shortages of prime feedstocks for ethylene manufacture have spawned numerous attempts to use alternate raw materials. Methane is one such raw material that is the most abundant component of natural gas, usually comprising up to --90 mole % of the hydrocarbon fraction, Thus, methane represents a considerably more abundant source for ethylene than ethane/propane, the two most widely used raw materials. Dehydrogenative coupling of methane requires temperatures in excess of 800 0 C for practical conversions along with a high endothermic heat of 53 Kcal/g mol - quite difficult to generate at temperatures of 0 C. Oxidative coupling removes the thermodynamic barrier of straight dehydrogenative coupling and heat-of-reaction problem. The primary objective of the early Union Carbide study was to uncover selective catalysts for coupling of methane to form C/sub 2/'s, and principally ethylene. Synthesis of ethylene (and some ethane) has been demonstrated by catalytic oxidative coupling of methane at atmospheric pressure and temperatures of 500 - 1000 0 C. A great number of metal oxides, supported on alpha-alumina support, have been screened for activity and selectivity in the normal, concurrent feeding mode of reactants, as well as, in the sequential or feed programming mode

  16. Catalytic combustion for the elimination of methane, BTEX and other VOC : IV

    International Nuclear Information System (INIS)

    Hayes, R.E.; Wanke, S.E.

    2008-01-01

    Options for volatile organic compound combustion include homogeneous combustion (flaring) or catalytic combustion involving a flameless combustion process that uses a solid catalyst to promote the combustion reaction. This presentation discussed relative reactivity testing for volatile organic compounds (VOCs) over commercial catalysts. Several commercial pad catalysts were tested, as well as other powders. The relative reactivity of methane as well as benzene, toluene, ethylbenzene, and xylene (BTEX) were investigated. The purpose of the project was to evaluate combustion of concentrated methane streams that contained BTEX compounds; evaluate catalytic combustion using a counter diffusive radiant heater; develop mathematical models for the reactor to enhance design and understanding; improve the catalyst for BTEX combustion; and target application-dehydrator units. Topics that were addressed in the presentation included methane and benzene conversion; catalytic radiant heaters; small industrial and commercial units; measured temperature distribution; fuel slippage, methane conversion; the effect of water and hydrocarbons; the effect of water-liquid injection; and water addition as vapour. Several observations were offered, including that high percentages of injected liquid water can reduce reactor operating temperature; combustion of BTEX remained highly efficient, however liquid injection could also cause temperature reductions and ultimately the reactor would extinguish; and pre-heating the feed can eliminate the temperature drop and pad wetness problem. It was concluded that BTEX compounds are reactive, and the technology appears promising. 19 figs

  17. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    Science.gov (United States)

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  18. Direct Activation Of Methane

    KAUST Repository

    Basset, Jean-Marie

    2013-07-15

    Heteropolyacids (HPAs) can activate methane at ambient temperature (e.g., 20.degree. C.) and atmospheric pressure, and transform methane to acetic acid, in the absence of any noble metal such as Pd). The HPAs can be, for example, those with Keggin structure: H.sub.4SiW.sub.12O.sub.40, H.sub.3PW.sub.12O.sub.40, H.sub.4SiMo.sub.12O.sub.40, or H.sub.3PMo.sub.12O.sub.40, can be when supported on silica.

  19. Australian methane fluxes

    International Nuclear Information System (INIS)

    Williams, D.J.

    1990-01-01

    Estimates are provided for the amount of methane emitted annually into the atmosphere in Australia for a variety of sources. The sources considered are coal mining, landfill, motor vehicles, natural gas suply system, rice paddies, bushfires, termites, wetland and animals. This assessment indicates that the major sources of methane are natural or agricultural in nature and therefore offer little scope for reduction. Nevertheless the remainder are not trival and reduction of these fluxes could play a significant part in any Australian action on the greenhouse problem. 19 refs., 7 tabs., 1 fig

  20. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  1. Dry reforming of methane with CO{sub 2} at elevated pressures

    Energy Technology Data Exchange (ETDEWEB)

    Milanov, A.; Schwab, E.; Wasserschaff, G. [BASF SE, Ludwigshafen (Germany); Schunk, S. [hte AG, Heidelberg (Germany)

    2013-11-01

    The indirect conversion of natural gas into higher value chemicals and fuels via syngas is superior with regard to efficiency compared to the currently available direct conversion technologies and remains the industrially preferred route. Typically the syngas production route is generally dictated by the H{sub 2}/CO ratio requirements of the downstream synthesis process. Processes such as direct DME synthesis, high-temperature Fischer-Tropsch and acetic acid synthesis require CO rich syngas that is not readily accessible by established technologies like steam methane reforming (SMR) and autothermal reforming of methane (ATR). The CO{sub 2} reforming of methane, also known as dry reforming (DRM), is an attractive alternative technology for the production of CO-rich syngas. This paper gives an overview of the current joint research activities at BASF and hte AG aiming to develop suitable catalysts for CO{sub 2} reforming of methane at elevated pressures with minimized input of process steam. The performance profiles of two newly developed base metal catalysts are presented and discussed. The catalysts exhibit high degrees of methane and CO{sub 2} conversion in combination with an extraordinary coking resistance under high severity process conditions. (orig.)

  2. Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Ikuno, Takaaki [Department; Zheng, Jian [Institute; Vjunov, Aleksei [Institute; Sanchez-Sanchez, Maricruz [Department; Ortuño, Manuel A. [Department; Pahls, Dale R. [Department; Fulton, John L. [Institute; Camaioni, Donald M. [Institute; Li, Zhanyong [Department; Ray, Debmalya [Department; Mehdi, B. Layla [Institute; Browning, Nigel D. [Institute; Materials; Farha, Omar K. [Department; Department; Hupp, Joseph T. [Department; Cramer, Christopher J. [Department; Gagliardi, Laura [Department; Lercher, Johannes A. [Department; Institute

    2017-07-17

    The catalyzed conversion of shale gas-derived light hydrocarbons, e.g. methane to methanol, for further application as automotive fuels and/or bulk chemicals is especially attractive in light of improved methods of hydrocarbon extraction. MOF based catalysts have previously been demonstrated to be active for a range of catalytic reactions. In this work we used Cu-NU1000 as a methane-to-methanol oxidation catalyst. In addition to product studies, in-situ X-ray Absorption Spectroscopic (XAS) experiments are performed under catalytic conditions in order to follow the modification of the Cu-species and directly probe the structure/activity properties of the Cu-NU1000 system. The insights reported herein serve as a first look at metal-organic framework materials as catalysts for methane oxidation and be the basis for development of the subsequent generations of materials.

  3. ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    K. Jothimurugesan; James G. Goodwin, Jr.; Santosh K. Gangwal

    1999-10-01

    Fischer-Tropsch (FT) synthesis to convert syngas (CO + H{sub 2}) derived from natural gas or coal to liquid fuels and wax is a well-established technology. For low H{sub 2} to CO ratio syngas produced from CO{sub 2} reforming of natural gas or from gasification of coal, the use of Fe catalysts is attractive because of their high water gas shift activity in addition to their high FT activity. Fe catalysts are also attractive due to their low cost and low methane selectivity. Because of the highly exothermic nature of the FT reaction, there has been a recent move away from fixed-bed reactors toward the development of slurry bubble column reactors (SBCRs) that employ 30 to 90 {micro}m catalyst particles suspended in a waxy liquid for efficient heat removal. However, the use of FeFT catalysts in an SBCR has been problematic due to severe catalyst attrition resulting in fines that plug the filter employed to separate the catalyst from the waxy product. Fe catalysts can undergo attrition in SBCRs not only due to vigorous movement and collisions but also due to phase changes that occur during activation and reaction.

  4. Methane synthesis under mild conditions for decentralized applications; Methansynthese unter milden Bedingungen fuer dezentrale Anwendungen

    Energy Technology Data Exchange (ETDEWEB)

    Schlueter, Michael [DBFZ Deutsches Biomasseforschungszentrum gGmbH, Leipzig (Germany); Roensch, Stefan

    2016-08-01

    It is a central aim of the German government to significantly reduce the emission of greenhouse gases in the next years. One possibility to reach this aim is the substitution of fossil fuels, especially natural gas, by fuels from biogenic sources (Bio-SNG). However, it is a drawback of Bio-SNG that the production costs are considerably higher than those of fossil natural gas. This work provides an approach to reduce the production costs of Bio-SNG. It is the aim to reduce the process parameters of the methane synthesis. At the same time, it has to be ensured that high methane yields are achieved even at those mild conditions. A procedure for the optimization of the methanation catalyst activity will be presented. If the catalyst is as active as possible even at mild conditions, it will be possible to produce Bio-SNG cost efficient even in small, decentralized scale.

  5. Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

    Science.gov (United States)

    Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

    2016-12-01

    This work focused on the catalytic transformation of methane (CH4) and carbon dioxide (CO2) into syngas (mixture of CO and H2). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400-700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

  6. Progresses in the stable isotope studies of microbial processes associated with wetland methane production

    International Nuclear Information System (INIS)

    Li Qing; Lin Guanghui

    2013-01-01

    Methane emissions from wetlands play a key role in regulating global atmospheric methane concentration, so better understanding of microbial processes for the methane emission in wetlands is critical for developing process models and reducing uncertainty in global methane emission inventory. In this review, we describe basic microbial processes for wetland methane production and then demonstrate how stable isotope fractionation and stable isotope probing can be used to investigate the mechanisms underlying different methanogenic pathways and to quantify microbial species involved in wetland methane production. When applying stable isotope technique to calculate contributions of different pathways to the total methane production in various wetlands, the technical challenge is how to determine isotopic fractionation factors for the acetate derived methane production and carbon dioxide derived methane production. Although the application of stable isotope probing techniques to study the actual functions of different microbial organisms to methane production process is significantly superior to the traditional molecular biology method, the combination of these two technologies will be crucial for direct linking of the microbial community and functional structure with the corresponding metabolic functions, and provide new ideas for future studies. (authors)

  7. Preparation and Performance Validation of Nano-Perovskite Type for Carbon Dioxide Reforming of Methane.

    Science.gov (United States)

    Kim, Taegyu; Park, Daeil

    2018-02-01

    This paper describes the La0.8Sr0.2NiO3 perovskite-type catalysts supported on α-Al2O3 that were prepared by polyol method and used as a catalyst for the carbon dioxide reforming of methane. The effect of the molar concentration of polyvinyl-pyrrolidone (PVP) on the reducibility, structural properties and carbon deposition was characterized by XRD, and TGA. The carbon dioxide reforming of methane on the catalyst was performed at the different concentration of PVP. At the 1 M PVP, main characteristic peaks of perovskite structure were established without impurities, thus showing the highest catalytic activity; 87.7% and 92.1% in CH4 and CO2 conversion, respectively. After the reaction, carbon deposition was 0.4-0.6%, while 6.2% on the existing Ni catalyst, indicating the perovskite-type catalyst has a superior characteristic preventing it from the carbon deposition at the carbon dioxide reforming of methane.

  8. Methane emissions from grasslands

    NARCIS (Netherlands)

    Pol - van Dasselaar, van den A.

    1998-01-01

    Introduction

    Methane (CH 4 ) is an important greenhouse gas. The concentration of greenhouse gases in the atmosphere has been increasing since pre-industrial times, mainly due to human activities. This increase gives concern,

  9. Development of Sulfur and Carbon Tolerant Reforming Alloy Catalysts Aided Fundamental Atomistic Insights

    Energy Technology Data Exchange (ETDEWEB)

    Suljo Linic

    2008-12-31

    Current hydrocarbon reforming catalysts suffer from rapid carbon and sulfur poisoning. Even though there is a tremendous incentive to develop more efficient catalysts, these materials are currently formulated using inefficient trial and error experimental approaches. We have utilized a hybrid experimental/theoretical approach, combining quantum Density Functional Theory (DFT) calculations and various state-of-the-art experimental tools, to formulate carbon tolerant reforming catalysts. We have employed DFT calculations to develop molecular insights into the elementary chemical transformations that lead to carbon poisoning of Ni catalysts. Based on the obtained molecular insights, we have identified, using DFT quantum calculation, various Ni alloy catalysts as potential carbon tolerant reforming catalysts. The alloy catalysts were synthesized and tested in steam reforming and partial oxidation of methane, propane, and isooctane. We demonstrated that the alloy catalysts are much more carbon-tolerant than monometallic Ni catalysts under nearly stoichiometric steam-to-carbon ratios. Under these conditions, monometallic Ni is rapidly poisoned by sp2 carbon deposits. The research approach is distinguished by two characteristics: (a) knowledge-based, bottomup approach, compared to the traditional trial and error approach, allows for a more efficient and systematic discovery of improved catalysts. (b) the focus is on exploring alloy materials which have been largely unexplored as potential reforming catalysts.

  10. New Trends in Gold Catalysts

    Directory of Open Access Journals (Sweden)

    Leonarda F. Liotta

    2014-07-01

    Full Text Available Gold is an element that has fascinated mankind for millennia. The catalytic properties of gold have been a source of debate, due to its complete chemical inertness when in a bulk form, while it can oxidize CO at temperatures as low as ~200 K when in a nanocrystalline state, as discovered by Haruta in the late 1980s [1]. Since then, extensive activity in both applied and fundamental research on gold has been initiated. The importance of the catalysis by gold represents one of the fasted growing fields in science and is proven by the promising applications in several fields, such as green chemistry and environmental catalysis, in the synthesis of single-walled carbon nanotubes, as modifiers of Ni catalysts for methane steam and dry reforming reactions and in biological and electrochemistry applications. The range of reactions catalyzed by gold, as well as the suitability of different supports and the influence of the preparation conditions have been widely explored and optimized in applied research [2]. Gold catalysts appeared to be very different from the other noble metal-based catalysts, due to their marked dependence on the preparation method, which is crucial for the genesis of the catalytic activity. Several methods, including deposition-precipitation, chemical vapor deposition and cation adsorption, have been applied for the preparation of gold catalysts over reducible oxides, like TiO2. Among these methods, deposition-precipitation has been the most frequently employed method for Au loading, and it involves the use of tetrachloroauric (III acid as a precursor. On the other hand, the number of articles dealing with Au-loaded acidic supports is smaller than that on basic supports, possibly because the deposition of [AuCl4]− or [AuOHxCl4−x]− species on acidic supports is difficult, due to their very low point of zero charge. Despite this challenge, several groups have reported the use of acidic zeolites as supports for gold. Zeolites

  11. Heat and Mass Transfer in a Reforming Catalyst Bed: Quantitative Evaluation of the Controlling Factor by Experiment

    Science.gov (United States)

    Usami, Yutaka; Fukusako, Shoichiro; Yamada, Masahiko

    Heat and mass transfer characteristics in a reforming catalyst bed have been experimentally investigated. Experiments were carried out with a single bench-scaled reforming tube which was filled with reforming catalyst. The tube wall was uniformly heated, and mixtures of steam and methane or propane were reformed through the catalyst bed. Most part of the reaction was completed in the upper part of the test tube. The effects of space velocity, which is a ratio of volumetric flow rate of process gas to the catalyst volume, steam carbon molar ratio, wall temperature, bed temperature, and catalyst particle diameter on the transport phenomena with chemical reaction, were determined. A correlation to heat transfer coefficient was determined by Nu, Rep, Pr, dp/d, and Da. The prediction of the overall methane conversion rate was also presented.

  12. Working group report: methane emissions from biomass burning

    International Nuclear Information System (INIS)

    Delmas, R.A.; Ahuja, D.

    1993-01-01

    Biomass burning is a significant source of atmospheric methane. Like most other sources of methane, it has both natural and anthropogenic causes, although anthropogenic causes now predominate. Most of the estimates of methane emissions from biomass burning in the past have relied on a uniform emission factor for all types of burning. This results in the share of trace gas emissions for different types of burning being the same as the amounts of biomass burned in those types. The Working Group endorsed the extension of an approach followed for Africa by Delmas et al. (1991) to use different emission factors for different types of biomass burning to estimate national emissions of methane. This is really critical as emission factors present important variations. While the focus of discussions of the Working Group was on methane emissions from biomass burning, the Group endorsed the IPCC-OECD methodology of estimating all greenhouse related trace gases from biomass burning. Neither the IPCC-OECD nor the methodology suggested here applies to estimation of trace gas emissions from the processing of biomass to upgraded fuels. They must be estimated separately. The Group also discussed technical options for controlling methane emissions from biomass. 12 refs

  13. Process heat exchanger with easy replacement of catalyst

    International Nuclear Information System (INIS)

    Jaeger, W.; Niemeyer, W.; Swars, H.

    1985-01-01

    The tubular furnace is used for the catalytic cracking of methane, where the heating gas helium comes from an HTR. The tubes can be heated from the inside and the catalytic material is liquid. The floor of the chamber accommodating the catalyst material has a double funnel shape. Locking valves are provided on the incoming and outgoing pipes for the nickel oxide granulate. (DG) [de

  14. Technology development for iron F-T catalysts. Final report

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-08-01

    The objectives of this work were twofold. The first objective was to design and construct a pilot plant for preparing precipitated iron oxide F-T precursors and demonstrate that the rate of production from this plant is equivalent to 100 lbs/day of dried metal oxide. Secondly, these precipitates were to be used to prepare catalysts capable of achieving 88% CO + H{sub 2} conversion with {le} 5 mole percent selectivity to methane + ethane.

  15. Various Transport Phenomena and Modeling in a Methane Reformer Duct for PEMFCs

    International Nuclear Information System (INIS)

    Jinliang Yuan; Fuan Ren; Jinliang Yuan; Bengt Sunden

    2006-01-01

    There are various physical processes (such as mass, heat and momentum transport) integrated with catalytic chemical reactions in a methane steam reforming duct. It is often found that endothermic and exothermic reactions in the ducts are strongly coupled by heat transfer from adjacent catalytic combustion ducts. In this paper, a three-dimensional calculation method is developed to simulate and analyze steam reforming of methane, and the effects on various transport processes in a steam reforming duct. The reformer conditions such as mass balances associated with the reforming reactions and gas permeation to/from the porous catalyst layer are applied in the analysis. The predicted results are presented and discussed for a composite duct consisting of a porous catalyst reaction area, the gas flow duct and solid layers. Parametric studies are conducted and the results show that the variables, such as fuel reformer temperatures and catalyst loadings, have significant effects on the transport processes and reformer performance. (authors)

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

    International Nuclear Information System (INIS)

    Engelmann Pirez, M.

    2004-12-01

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

  17. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst

    Directory of Open Access Journals (Sweden)

    Istadi Istadi

    2011-11-01

    Full Text Available Major problem in CO2 reforming of methane (CORM process is coke formation which is a carbonaceous residue that can physically cover active sites of a catalyst surface and leads to catalyst deactivation. A key to develop a more coke-resistant catalyst lies in a better understanding of the methane reforming mechanism at a molecular level. Therefore, this paper is aimed to simulate a micro-kinetic approach in order to calculate coking rate in CORM reaction. Rates of encapsulating and filamentous carbon formation are also included. The simulation results show that the studied catalyst has a high activity, and the rate of carbon formation is relatively low. This micro-kinetic modeling approach can be used as a tool to better understand the catalyst deactivation phenomena in reaction via carbon deposition. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 10th May 2011; Revised: 16th August 2011; Accepted: 27th August 2011[How to Cite: I. Istadi, D.D. Anggoro, N.A.S. Amin, and D.H.W. Ling. (2011. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 129-136. doi:10.9767/bcrec.6.2.1213.129-136][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.2.1213.129-136 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/1213 ] | View in  |  

  18. FY 1998 Report on technical results. Part 1 of 2. Research and development of supersonic transportation aircraft propulsion systems (Development of methane-fueled aircraft engines); 1998 nendo choonsoku yusokiyo suishin system no kenkyu kaihatsu seika hokokusho. 1/2. Methane nenryo kokukiyo engine no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-09-01

    The research and development project is conducted for (1) ramjet systems, (2) high-performance turbojet systems, (3) instrumentation/control systems and (4) total systems, in order to develop methane-fueled supersonic transportation aircraft engines. For the item (1), the ram combustor for the target engine is designed to evaluate its performance, and the shock-position within the dummy intake is successfully controlled by the variable exhaust nozzle. For the item (2), the R and D efforts are directed to the fans and low-pressure turbines, the former covering the studies on the single-stage elements for the fans of high flow rate, and the elements for the 2-stage, high-efficiency, high-load fans. For the item (3), the R and D efforts are directed to the electronic control systems and electro-optical measurement systems, the latter including development of the improved optical positioning and rotational sensors operating at high temperature of 350 degrees C. For the item (4), the R and D efforts are directed to intake nozzles as the total system component, noise reduction technology, and cooling and new material application technologies. (NEDO)

  19. Direct catalytic conversion of methane and light hydrocarbon gases. Final report, October 1, 1986--July 31, 1989

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee-Wai

    1995-06-01

    This project explored conversion of methane to useful products by two techniques that do not involve oxidative coupling. The first approach was direct catalytic dehydrocoupling of methane to give hydrocarbons and hydrogen. The second approach was oxidation of methane to methanol by using heterogenized versions of catalysts that were developed as homogeneous models of cytochrome-P450, an enzyme that actively hydroxylates hydrocarbons by using molecular oxygen. Two possibilities exist for dehydrocoupling of methane to higher hydrocarbons: The first, oxidative coupling to ethane/ethylene and water, is the subject of intense current interest. Nonoxidative coupling to higher hydrocarbons and hydrogen is endothermic, but in the absence of coke formation the theoretical thermodynamic equilibrium yield of hydrocarbons varies from 25% at 827{degrees}C to 65% at 1100{degrees}C (at atmospheric pressure). In this project we synthesized novel, highly dispersed metal catalysts by attaching metal clusters to inorganic supports. The second approach mimics microbial metabolism of methane to produce methanol. The methane mono-oxygenase enzyme responsible for the oxidation of methane to methanol in biological systems has exceptional selectivity and very good rates. Enzyme mimics are systems that function as the enzymes do but overcome the problems of slow rates and poor stability. Most of that effort has focused on mimics of cytochrome P-450, which is a very active selective oxidation enzyme and has a metalloporphyrin at the active site. The interest in nonporphyrin mimics coincides with the interest in methane mono-oxygenase, whose active site has been identified as a {mu}-oxo dinuclear iron complex.We employed mimics of cytochrome P-450, heterogenized to provide additional stability. The oxidation of methane with molecular oxygen was investigated in a fixed-bed, down-flow reactor with various anchored metal phthalocyanines (PC) and porphyrins (TPP) as the catalysts.

  20. A facile method for the preparation of Covalent Triazine Framework coated monoliths as catalyst support - applications in C1 catalysis

    KAUST Repository

    Bavykina, Anastasiya V.

    2017-07-17

    A quasi Chemical Vapour Deposition method for the manufacturing of well-defined Covalent Triazine Framework (CTF) coatings on cordierite monoliths is reported. The resulting supported porous organic polymer is an excellent support for the immobilisation of two different homogeneous catalysts: 1) an IrIIICp*-based catalyst for the hydrogen production from formic acid, and 2) a PtII-based for the direct activation of methane via Periana chemistry. The immobilised catalysts display a much higher activity in comparison with the unsupported CTF operated in slurry because of improved mass transport. Our results demonstrate that CTF based catalysts can be further optimised by engineering at different length-scales.

  1. Methods of making textured catalysts

    Science.gov (United States)

    Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

    2010-08-17

    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  2. Catalyst Alloys Processing

    Science.gov (United States)

    Tan, Xincai

    2014-10-01

    Catalysts are one of the key materials used for diamond formation at high pressures. Several such catalyst products have been developed and applied in China and around the world. The catalyst alloy most widely used in China is Ni70Mn25Co5 developed at Changsha Research Institute of Mining and Metallurgy. In this article, detailed techniques for manufacturing such a typical catalyst alloy will be reviewed. The characteristics of the alloy will be described. Detailed processing of the alloy will be presented, including remelting and casting, hot rolling, annealing, surface treatment, cold rolling, blanking, finishing, packaging, and waste treatment. An example use of the catalyst alloy will also be given. Industrial experience shows that for the catalyst alloy products, a vacuum induction remelt furnace can be used for remelting, a metal mold can be used for casting, hot and cold rolling can be used for forming, and acid pickling can be used for metal surface cleaning.

  3. Project identification for methane reduction options

    Energy Technology Data Exchange (ETDEWEB)

    Kerr, T.

    1996-12-31

    This paper discusses efforts directed at reduction in emission of methane to the atmosphere. Methane is a potent greenhouse gas, which on a 20 year timeframe may present a similar problem to carbon dioxide. In addition, methane causes additional problems in the form of smog and its longer atmospheric lifetime. The author discusses strategies for reducing methane emission from several major sources. This includes landfill methane recovery, coalbed methane recovery, livestock methane reduction - in the form of ruminant methane reduction and manure methane recovery. The author presents examples of projects which have implemented these ideas, the economics of the projects, and additional gains which come from the projects.

  4. ECOS E-MATRIX Methane and Volatile Organic Carbon (VOC) Emissions Best Practices Database

    Energy Technology Data Exchange (ETDEWEB)

    Parisien, Lia [The Environmental Council Of The States, Washington, DC (United States)

    2016-01-31

    This final scientific/technical report on the ECOS e-MATRIX Methane and Volatile Organic Carbon (VOC) Emissions Best Practices Database provides a disclaimer and acknowledgement, table of contents, executive summary, description of project activities, and briefing/technical presentation link.

  5. Alloy catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel alloy catalyst material for use in the synthesis of hydrogen peroxide from oxygen and hydrogen, or from oxygen and water. The present invention also relates to a cathode and an electrochemical cell comprising the novel catalyst material, and the process use...... of the novel catalyst material for synthesising hydrogen peroxide from oxygen and hydrogen, or from oxygen and water....

  6. Methane emissions from grasslands

    OpenAIRE

    Pol - van Dasselaar, van den, A.

    1998-01-01

    Introduction

    Methane (CH 4 ) is an important greenhouse gas. The concentration of greenhouse gases in the atmosphere has been increasing since pre-industrial times, mainly due to human activities. This increase gives concern, because it may cause global warming due to an enhanced greenhouse effect.

    In the soil, CH 4 may be produced under anaerobic conditions, and consumed under aero...

  7. Coal Bed Methane Primer

    Energy Technology Data Exchange (ETDEWEB)

    Dan Arthur; Bruce Langhus; Jon Seekins

    2005-05-25

    During the second half of the 1990's Coal Bed Methane (CBM) production increased dramatically nationwide to represent a significant new source of income and natural gas for many independent and established producers. Matching these soaring production rates during this period was a heightened public awareness of environmental concerns. These concerns left unexplained and under-addressed have created a significant growth in public involvement generating literally thousands of unfocused project comments for various regional NEPA efforts resulting in the delayed development of public and fee lands. The accelerating interest in CBM development coupled to the growth in public involvement has prompted the conceptualization of this project for the development of a CBM Primer. The Primer is designed to serve as a summary document, which introduces and encapsulates information pertinent to the development of Coal Bed Methane (CBM), including focused discussions of coal deposits, methane as a natural formed gas, split mineral estates, development techniques, operational issues, producing methods, applicable regulatory frameworks, land and resource management, mitigation measures, preparation of project plans, data availability, Indian Trust issues and relevant environmental technologies. An important aspect of gaining access to federal, state, tribal, or fee lands involves education of a broad array of stakeholders, including land and mineral owners, regulators, conservationists, tribal governments, special interest groups, and numerous others that could be impacted by the development of coal bed methane. Perhaps the most crucial aspect of successfully developing CBM resources is stakeholder education. Currently, an inconsistent picture of CBM exists. There is a significant lack of understanding on the parts of nearly all stakeholders, including industry, government, special interest groups, and land owners. It is envisioned the Primer would being used by a variety of

  8. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Final technical report, Volume 1 - effects of solvents, catalysts and temperature conditions on conversion and structural changes of low-rank coals

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Lili [Pennsylvania State Univ., University Park, PA (United States); Schobert, Harold H. [Pennsylvania State Univ., University Park, PA (United States); Song, Chunshan [Pennsylvania State Univ., University Park, PA (United States)

    1998-01-01

    The main objectives of this project were to study the effects of low-temperature pretreatments on coal structure and their impacts on subsequent liquefaction. The effects of pretreatment temperatures, catalyst type, coal rank, and influence of solvent were examined. Specific objectives were to identify the basic changes in coal structure induced by catalytic and thermal pretreatments, and to determine the reactivity of the catalytically and thermally treated coals for liquefaction. In the original project management plan it was indicated that six coals would be used for the study. These were to include two each of bituminous, subbituminous, and lignite rank. For convenience in executing the experimental work, two parallel efforts were conducted. The first involved the two lignites and one subbituminous coal; and the second, the two bituminous coals and the remaining subbituminous coal. This Volume presents the results of the first portion of the work, studies on two lignites and one subbituminous coal. The remaining work accomplished under this project will be described and discussed in Volume 2 of this report. The objective of this portion of the project was to determine and compare the effects of solvents, catalysts and reaction conditions on coal liquefaction. Specifically, the improvements of reaction conversion, product distribution, as well as the structural changes in the coals and coal-derived products were examined. This study targeted at promoting hydrogenation of the coal-derived radicals, generated during thermal cleavage of chemical bonds, by using a good hydrogen donor-solvent and an effective catalyst. Attempts were also made in efforts to match the formation and hydrogenation of the free radicals and thus to prevent retrogressive reaction.

  9. METHOD OF PURIFYING CATALYSTS

    Science.gov (United States)

    Joris, G.G.

    1958-09-01

    It has been fuund that the presence of chlorine as an impurity adversely affects the performance of finely divided platinum catalysts such as are used in the isotopic exchange process for the production of beavy water. This chlorine impurity may be removed from these catalysts by treating the catalyst at an elevated temperature with dry hydrogen and then with wet hydrogen, having a hydrogen-water vapor volume of about 8: 1. This alternate treatment by dry hydrogen and wet hydrogen is continued until the chlorine is largely removed from the catalyst.

  10. Genomic selection for methane emission

    DEFF Research Database (Denmark)

    de Haas, Yvette; Pryce, Jennie E; Wall, Eileen

    2016-01-01

    Climate change is a growing area of international concern, and it is well established that the release of greenhouse gases (GHG) is a contributing factor. Of the various GHG produced by ruminants, enteric methane (CH4 ) is the most important contributor. One mitigation strategy is to reduce methane...... emission through genetic selection. Our first attempt used beef cattle and a GWAS to identify genes associated with several CH4 traits in Angus beef cattle. The Angus population consisted of 1020 animals with phenotypes on methane production (MeP), dry matter intake (DMI), and weight (WT). Additionally......, two new methane traits: residual genetic methane (RGM) and residual phenotypic methane (RPM) were calculated by adjusting CH4 for DMI and WT. Animals were genotyped using the 800k Illumina Bovine HD Array. Estimated heritabilities were 0.30, 0.19 and 0.15 for MeP, RGM and RPM respectively...

  11. Catalytic conversion of methane to methanol using Cu-zeolites.

    Science.gov (United States)

    Alayon, Evalyn Mae C; Nachtegaal, Maarten; Ranocchiari, Marco; van Bokhoven, Jeroen A

    2012-01-01

    The conversion of methane to value-added liquid chemicals is a promising answer to the imminent demand for fuels and chemical synthesis materials in the advent of a dwindling petroleum supply. Current technology requires high energy input for the synthesis gas production, and is characterized by low overall selectivity, which calls for alternative reaction routes. The limitation to achieve high selectivity is the high C-H bond strength of methane. High-temperature reaction systems favor gas-phase radical reactions and total oxidation. This suggests that the catalysts for methane activation should be active at low temperatures. The enzymatic-inspired metal-exchanged zeolite systems apparently fulfill this need, however, methanol yield is low and a catalytic process cannot yet be established. Homogeneous and heterogeneous catalytic systems have been described which stabilize the intermediate formed after the first C-H activation. The understanding of the reaction mechanism and the determination of the active metal sites are important for formulating strategies for the upgrade of methane conversion catalytic technologies.

  12. Reduction of Nitrogen Oxides using zeolite catalysts exchanged with cobalt

    International Nuclear Information System (INIS)

    Garcia M, E.A.; Bustamante L, F.; Montes de C, C.

    1999-01-01

    The Selective Catalytic Reduction (SCR) of NOx by methane in excess oxygen was studied over several zeolite catalysts; namely cobalt loaded mordenite, ferrierite, SM-5 and the corresponding acid forms. When NO2 predominated n the NOx mixture the acid forms showed the highest N2 formation rates under dry conditions. Mordenite supported catalysts were the most active ones followed by ferrierite and ZSM-5. The most active Co-Mordenite catalyst was tested using a NOx mixture, containing mostly NO, under dry conditions and in the presence of water and SO2. The addition of 8 % water to the reaction mixture lead to a reversible deactivation, mainly at low temperatures. When the reaction mixture contained 60 ppm SO2, the N2 formation rate decreased about a half likely due to SO2 poisoning

  13. Dry Reforming of Methane Using a Nickel Membrane Reactor

    Directory of Open Access Journals (Sweden)

    Jonas M. Leimert

    2017-12-01

    Full Text Available Dry reforming is a very interesting process for synthesis gas generation from CH 4 and CO 2 but suffers from low hydrogen yields due to the reverse water–gas shift reaction (WGS. For this reason, membranes are often used for hydrogen separation, which in turn leads to coke formation at the process temperatures suitable for the membranes. To avoid these problems, this work shows the possibility of using nickel self-supported membranes for hydrogen separation at a temperature of 800 ∘ C. The higher temperature effectively suppresses coke formation. The paper features the analysis of the dry reforming reaction in a nickel membrane reactor without additional catalyst. The measurement campaign targeted coke formation and conversion of the methane feedstock. The nickel approximately 50% without hydrogen separation. The hydrogen removal led to an increase in methane conversion to 60–90%.

  14. Creating Methane from Plastic: Recycling at a Lunar Outpost

    Science.gov (United States)

    Santiago-Maldonado, Edgardo; Captain, Janine; Devor, Robert; Gleaton, Jeremy

    2010-01-01

    The high cost of re-supply from Earth demands resources to be utilized to the fullest extent for exploration missions. The ability to refuel on the lunar surface would reduce the vehicle mass during launch and provide excess payload capability. Recycling is a key technology that maximizes the available resources by converting waste products into useful commodities. One example of this is to convert crew member waste such as plastic packaging, food scraps, and human waste into fuel. This process thermally degrades plastic in the presence of oxygen producing CO2 and CO. The CO2 and CO are then reacted with hydrogen over catalyst (Sabatier reaction) producing methane. An end-to-end laboratory-scale system has been designed and built to produce methane from plastic, in this case polyethylene. This first generation system yields 12-16% CH4 by weight of plastic used.

  15. Hydroxide catalysts for lignin depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T; Biddy, Mary J.; Kruger, Jacob S.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-10-17

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  16. Hydroxide catalysts for lignin depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-04-25

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  17. Investigation on deactivation and regeneration of a commercial Ni/Al{sub 2}O{sub 3} catalyst in coal volatile decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Li, L.; Ozaki, J.; Morishita, K.; Ida, C.; Takei, M.; Takarada, T. [Gunma Industrial Support Organization, Gumma (Japan)

    2008-09-15

    The deactivation mechanism of a commercial Ni/Al{sub 2}O{sub 3} catalyst used during coal volatile decomposition was investigated by transmission electron microscopy-energy dispersive X-ray spectroscopy (TEMEDS), X-ray diffraction (XRD) and nitrogen adsorption. The existence of carbonous species in the reaction system promoted nickel particle growth during coal volatile decomposition, and subsequent coking from volatile cracking. Throughout the catalyst deactivation tests, coke deposits were observed as encapsulating carbon in the spent catalyst, and nickel particles doubled in size from around 10 to 20 mm. The spent catalyst was regenerated in oxygen at relatively moderate conditions by removing the coke deposits. As a result, the catalyst activity was restored remarkably; 1.7 times the surface area and double pore volume were present in the regenerated catalyst compared to the spent catalyst. Also, the regenerated catalyst showed high activity for coal volatile decomposition. Under catalysis of the regenerated Ni/Al{sub 2}O{sub 3} the tarry material in coal volatile matter could transform much more completely, gaining both high gas yields and high carbon balance. We also found that methanation is structure sensitive to nickel particles. Under the action of the regenerated catalyst, CO formed during coal volatile decomposition could not be further converted into methane, and the product gases provided a higher CO concentration. Noticeably, tar decomposition was confirmed to be less structure sensitive to the nickel particles than CO-methanation.

  18. DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

    International Nuclear Information System (INIS)

    Bukur, Dragomir B.; Lang, X.; Chokkaram, S.; Nowicki, L.; Wei, G.; Ding, Y.; Reddy, B.; Xiao, S.

    1999-01-01

    Despite the current worldwide oil glut, the US will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer-Tropsch (F-T) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Some of the F-T catalysts synthesized and tested at Texas A and M University under DOE Contract No. DE-AC22-89PC89868 were more active than any other known catalysts developed for maximizing production of high molecular weight hydrocarbons (waxes). The objectives of the present contract were to demonstrate repeatability of catalyst performance and reproducibility of preparation procedures of two of these catalysts on a laboratory scale. Improvements in the catalyst performance were attempted through the use of: (a) higher reaction pressure and gas space velocity to maximize the reactor productivity; (b) modifications in catalyst preparation steps; and (c) different pretreatment procedures. Repeatability of catalyst performance and reproducibility of catalyst synthesis procedure have been successfully demonstrated in stirred tank slurry reactor tests. Reactor space-time-yield was increased up to 48% by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while maintaining the gas contact time and synthesis gas conversion at a constant value. Use of calcination temperatures above 300 C, additional CaO promoter, and/or potassium silicate as the source of potassium promoter, instead of potassium bicarbonate, did not result in improved catalyst performance. By using different catalyst activation procedures they were able to increase substantially the catalyst activity, while maintaining low methane and gaseous hydrocarbon selectivities. Catalyst productivity in runs SA-0946 and SA-2186 was 0.71 and 0.86 gHC/g-Fe/h, respectively, and this represents 45-75% improvement in productivity relative to that achieved in Rheinpreussen's demonstration plant

  19. Precious metal compounds and recovery. Fischer-Tropsch catalysts and catalysts for hydroformylation and oxo processes

    Energy Technology Data Exchange (ETDEWEB)

    Schapp, J.; Arndt, M. [W.C. Heraeus GmbH, Hanau (Germany); Meyer, H. [Heraeus Metal Processing Inc., Santa Fe Springs, CA (United States)

    2006-07-01

    Solid-phase Fischer-Tropsch catalysts, which are used in the emerging field of interest known as ''Gas-to-Liquid'' (GTL), consist to a high percentage of cobalt. In addition, they contain on a value basis, a considerable amount of platinum group metals or rhenium as promoters. Therefore, there is an imperative need for economically feasible recycling processes triggered not only by the value of the metals in spent Fischer-Tropsch catalysts, but also by the potentially limited availability of promoters like rhenium. Heraeus, as a precious metal expert, is supporting this important technology with its profound know-how in developing tailor-made hydrometallurgical recycling processes for all kinds of catalyst systems. Besides giving an overview of state-of-the-art recovery processes, this paper will clarify the economic and environmental aspects involved. Hydroformylation and oxo processes are technologies which consume a major percentage of homogeneous catalysts worldwide. The focus lies on organometallic compounds with rhodium as the catalytic center. With significant rises of the rhodium price, many companies are being pushed to look more closely at the involved recycling terms. Accordingly, Heraeus is proud to offer its HeraCYCLE {sup registered} recovery process recently developed for homogeneous catalysts in particular. Furthermore, Heraeus manufactures the required quantities of fresh homogeneous catalysts ensuring highest quality standards. Key economic, technical, and environmental aspects of the precious metal loops will be covered by this paper. (orig.)

  20. Methanization of industrial liquid effluents

    International Nuclear Information System (INIS)

    Frederic, S.; Lugardon, A.

    2007-01-01

    In a first part, this work deals with the theoretical aspects of the methanization of the industrial effluents; the associated reactional processes are detailed. The second part presents the technological criteria for choosing the methanization process in terms of the characteristics of the effluent to be treated. Some of the methanization processes are presented with their respective advantages and disadvantages. At last, is described the implementation of an industrial methanization unit. The size and the main choices are detailed: the anaerobic reactor, the control, the valorization aspects of the biogas produced. Some examples of industrial developments illustrate the different used options. (O.M.)

  1. Methane emissions from coal mining

    International Nuclear Information System (INIS)

    Boyer, C.M.; Kelafant, J.R.; Kuuskraa, V.A.; Manger, K.C.; Kruger, D.

    1990-09-01

    The report estimates global methane emissions from coal mining on a country specific basis, evaluates the technologies available to degasify coal seams and assesses the economics of recovering methane liberated during mining. 33 to 64 million tonnes were liberated in 1987 from coal mining, 75 per cent of which came from China, the USSR, Poland and the USA. Methane emissions from coal mining are likely to increase. Emission levels vary between surface and underground mines. The methane currently removed from underground mines for safety reasons could be used in a number of ways, which may be economically attractive. 55 refs., 19 figs., 24 tabs

  2. Hydrogen purification by selective methanation of CO in CO/CO2/H2

    DEFF Research Database (Denmark)

    Andersen, Anne Mette; Johannessen, Tue; Livbjerg, Hans

    Normally, the hydrogen-rich feed gas to PEM Fuel Cells has a relatively high concentration of CO, which is poisonous to the anode catalyst. CO can be removed by selective oxidation or by methanation. For methanation, it is desired to minimize the use of hydrogen by selectively removing the CO...... without “loosing” hydrogen by methanating CO2. Studies have shown that CO has an inhibiting effect on the methanation of CO2. This inhibiting effect is thought to influence the selective methanation of CO. The aim of this project has been to remove CO from a process gas containing H2, CO and CO2......: Methanation of CO and the reverse water gas shift reaction: (1) CO + 3H2 -> CH4 + H2O (2) CO2 + H2 -> CO + H2O In experiments with only CO2 and hydrogen in the feed gas there is a significant production of CO and methane. The concentration of CO in the reactor rapidly reaches a level, where it inhibits (or...

  3. Catalytic Methane Decomposition over Fe-Al2O3

    KAUST Repository

    Zhou, Lu

    2016-05-09

    The presence of a Fe-FeAl2O4 structure over an Fe-Al2O3 catalysts is demonstrated to be vital for the catalytic methane decomposition (CMD) activity. After H2 reduction at 750°C, Fe-Al2O3 prepared by means of a fusion method, containing 86.5wt% FeAl2O4 and 13.5wt% Fe0, showed a stable CMD activity at 750°C for as long as 10h. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Development of Augmented Spark Impinging Igniter System for Methane Engines

    Science.gov (United States)

    Marshall, William M.; Osborne, Robin J.; Greene, Sandra E.

    2017-01-01

    The Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) program is establishing multiple no-funds-exchanged Space Act Agreement (SAA) partnerships with U.S. private sector entities. The purpose of this program is to encourage the development of robotic lunar landers that can be integrated with U.S. commercial launch capabilities to deliver payloads to the lunar surface. As part of the efforts in Lander Technologies, NASA Marshall Space Flight Center (MSFC) is developing liquid oxygen (LOX) and liquid methane (LCH4) engine technology to share with the Lunar CATALYST partners. Liquid oxygen and liquid methane propellants are attractive owing to their relatively high specific impulse for chemical propulsion systems, modest storage requirements, and adaptability to NASA's Journey to Mars plans. Methane has also been viewed as a possible propellant choice for lunar missions, owing to the performance benefits and as a technology development stepping stone to Martian missions. However, in the development of methane propulsion, methane ignition has historically been viewed as a high risk area in the development of such an engine. A great deal of work has been conducted in the past decade devoted to risk reduction in LOX/CH4 ignition. This paper will review and summarize the history and results of LOX/CH4 ignition programs conducted at NASA. More recently, a NASA-developed Augmented Spark Impinging (ASI) igniter body, which utilizes a conventional spark exciter system, is being tested with LOX/CH4 to help support internal and commercial engine development programs, such as those in Lunar CATALYST. One challenge with spark exciter systems, especially at altitude conditions, is the ignition lead that transmits the high voltage pulse from the exciter to the spark igniter (spark plug). The ignition lead can be prone to corona discharge, reducing the energy delivered by the spark and potentially causing non-ignition events. For the current work, a

  5. Nickel metal with various morphologies: synthesis and performances for catalytic carbon dioxide reforming with methane.

    Science.gov (United States)

    Teabpinyok, Nopporn; Samingprai, Sutheerawat; Chareonpanich, Metta

    2012-12-01

    In this research, nickel metal of three different morphologies including nanostar, icosahedra, and microsphere structures were synthesized. It was found nanostar nickel revealed the Ni(111) crystallographic plane with particle size in the range of 150-200 nm and BET surface area of 13 m2/g. The icosahedra nickel also showed the Ni(111) crystallographic plane with larger particle size (300-400 nm) and BET surface area of 20 m2/g, whereas microsphere nickel exhibited the relatively large cluster size (approximately 3 microm) and BET surface area (114 m2/g) as a result of an aggregation of Ni(101) nanoplates. The obtained nickel catalysts were tested for the activity in carbon dioxide reforming with methane. Based on the similar specific surface area of catalysts, nanostar nickel showed the highest carbon dioxide and methane conversions due to its crystallographic structure. At 700 degrees C, nanostar nickel catalyst exhibited the highest carbon dioxide and methane conversions of 17.6 and 10.5 times higher than those of microsphere nickel catalyst, respectively.

  6. Magnetic catalyst bodies

    NARCIS (Netherlands)

    Teunissen, Wendy; Bol, A.A.; Geus, John W.

    1999-01-01

    After a discussion about the importance of the size of the catalyst bodies with reactions in the liquid-phase with a suspended catalyst, the possibilities of magnetic separation are dealt with. Deficiencies of the usual ferromagnetic particles are the reactivity and the clustering of the

  7. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  8. Nanostructured catalyst supports

    Science.gov (United States)

    Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

    2012-10-02

    The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

  9. Catalyst for hydrocarbon conversion

    International Nuclear Information System (INIS)

    Duhaut, P.; Miquel, J.

    1975-01-01

    A description is given for a catalyst and process for hydrocarbon conversions, e.g., reforming. The catalyst contains an alumina carrier, platinum, iridium, at least one metal selected from uranium, vanadium, and gallium, and optionally halogen in the form of metal halide of one of the aforesaid components. (U.S.)

  10. Ni catalyst wash-coated on metal monolith with enhanced heat-transfer capability for steam reforming

    Science.gov (United States)

    Ryu, Jae-Hong; Lee, Kwan-Young; La, Howon; Kim, Hak-Joo; Yang, Jung-Il; Jung, Heon

    A commercial Ni-based catalyst is wash-coated on a monolith made of 50 μm-thick fecralloy plates. Compared with the same volume of coarsely powdered Ni catalysts, the monolith wash-coated Ni catalysts give higher methane conversion in the steam reforming reaction, especially at gas hourly space velocities (GHSV) higher than 28,000 h -1, and with no pressure drop. A higher conversion of the monolith catalyst is obtained, even though it contains a lower amount of active catalyst (3 g versus 17 g for a powdered catalyst), which indicates that the heat-transfer capability of the wash-coated Ni catalyst is significantly enhanced by the use of a metal monolith. The efficacy of the monolith catalyst is tested using a shell-and-tube type heat-exchanger reactor with 912 cm 3 of the monolith catalyst charged on to the tube side and hot combusted gas supplied to the shell side in a counter-current direction to the reactant flow. A methane conversion greater than 94% is obtained at a GHSV of 7300 h -1 and an average temperature of 640 °C. Nickel catalysts should first be reduced to become active for steam reforming. Doping a small amount (0.12 wt.%) of noble metal (Ru or Pt) in the commercial Ni catalyst renders the wash-coated catalyst as active as a pre-reduced Ni catalyst. Thus, noble metal-doped Ni appears useful for steam reforming without any pre-reduction procedure.

  11. A transient kinetic study of nickel-catalyzed methanation: Final report

    International Nuclear Information System (INIS)

    Hoost, T.E.; Goodwin, J.G. Jr.

    1988-11-01

    The results of this study are in two major parts. In Part I the use of steady-state isotopic transients of multiple elements (C, H, and O) under actual methanation reaction conditions has permitted an assessment of the reactivity of water on a Ni powder catalyst. It was concluded based on the addition of isotopic water that oxygen, once reacted to form water, is able to readsorb even where the surface coverage of CO remains high. At the low relative partial pressures of water used, however, there was no effect of added water on the formation of methane. The surface residence time of water determined from isotopic transients contains the residence time on the surface during the primary formation reaction as well as the time spent during readsorption(s). Part II addressed how a catalyst modifier (in this case Cl) affects methanation in CO hydrogenation using steady-state isotopic transient kinetic analysis (SSITKA) of methanation. The results obtained using silica-supported Ru suggest the structural rearrangements induced by the presence of chlorine, rather than selective site blocking or electronic interactions, may be the primary mechanism of chlorine modification of the catalytic properties of supported metals for CO hydrogenation. SSITKA indicated that the decrease in methanation activity with increasing initial Cl concentration was a function of a decrease in the number of reactive surface intermediates (or sites) and not of a change in site activity. 36 refs., 10 figs., 5 tabs

  12. Methane from wood

    International Nuclear Information System (INIS)

    Schulz, T. F.; Barreto, L.; Kypreos, S.; Stucki, S.

    2005-07-01

    The role of wood-based energy technologies in the Swiss energy system in the long-term is examined using the energy-system Swiss MARKAL model. The Swiss MARKAL model is a 'bottom-up' energy-systems optimization model that allows a detailed representation of energy technologies. The model has been developed as a joint effort between the Energy Economics Group (EEG) at Paul Scherrer Institute PSI) and the University of Geneva and is currently used at PSI-EEG. Using the Swiss MARKAL model, this study examines the conditions under which wood-based energy technologies could play a role in the Swiss energy system, the most attractive pathways for their use and the policy measures that could support them. Given the involvement of PSI in the ECOGAS project, especial emphasis is put on the production of bio-SNG from wood via gasification and methanation of syngas and on hydrothermal gasification of woody biomass. Of specific interest as weIl is the fraction of fuel used in passenger cars that could be produced by locally harvested wood. The report is organized as follows: Section 2 presents a brief description of the MARKAL model. Section 3 describes the results of the base case scenario, which represents a plausible, 'middle-of-the-road' development of the Swiss energy system. Section 4 discusses results illustrating the conditions under which the wood-based methanation technology could become competitive in the Swiss energy market, the role of oil and gas prices, subsidies to methanation technologies and the introduction of a competing technology, namely the wood-based Fischer-Tropsch synthesis. FinaIly, section 5 outlines some conclusions from this analysis. (author)

  13. Recovering platinum-group metals from auto catalysts

    International Nuclear Information System (INIS)

    Hoffmann, J.E.

    1988-01-01

    A variety of technical challenges confront the prospective processor of spent automotive catalysts, including a frequently high (1-10%) lead content; the presence of alumina in both soluble, γ, and insoluble, α, forms; the need for recovery of greater than 90% to assure an economical process; the disposition and control of process effluents, refractory residues, and lead metal salts from catalyst processing; and the highly aggressive and corrosive reagents required. Six different processes for recovery of platinum, palladium and rhodium are described and compared on the basis of their utility and how well they meet these technical challenges

  14. Catalysis mechanism of Pd-promoted γ-alumina in the thermal decomposition of methane to hydrogen: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Salam, M. Abdus; Abdullah, Bawadi, E-mail: bawadi_abdullah@utp.edu.my

    2017-02-15

    Thermo-catalytic methane decomposition to elemental hydrogen mechanism in transitional metals (Pd, Ni & Mo) promoted Al{sub 2}O{sub 3} (001) catalyst have been studied using the density functional theory (DFT). Decomposition reactions are spontaneous and favourable above 775 K for all promoter. Pd-promoted Al{sub 2}O{sub 3} (001) catalyst demonstrates a breakthrough decomposition activity in hydrogen production as compared to Ni− and Mo-promoted Al{sub 2}O{sub 3} (001) catalysts. The activation energy (E{sub a}) range of the catalysis for Pd promoted Al{sub 2}O{sub 3} (001) catalysts is 0.003–0.34 eV. Whereas, Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts display activation energy E{sub a} in the range of 0.63–1.15 eV and 0.04–5.98 eV, respectively. Pd-promoted catalyst also shows a higher adsorption energy (−0.68 eV) and reactivity than that of Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts. The rates of successive decomposition of methane are found to be 16.15 × 10{sup 12}, 15.95 × 10{sup 12} and 16.09 × 10{sup 12} s{sup −1} for the promoter of Pd, Ni and Mo, respectively. Pd promoted Al{sub 2}O{sub 3} (001) catalyst reduces the methane decomposition temperature (775 K) and deactivation rate significantly. The catalytic conditions and catalyst is promising in producing hydrogen to support hydrogen economy. - Highlights: • Transition metals (Pd, Ni & Mo) promoted γ-alumina catalysts are designed successfully. • Pd-promoted catalyst showed breakthrough activity in methane decomposition to hydrogen. • DFT study explored the catalysis mechanism of methane decomposition at atomic level. • Pd-promoted catalyst reduced temperature and activation barrier of methane decomposition reaction significantly.

  15. Tetrakis(dimethoxyboryl)methane

    OpenAIRE

    Sumeng Liu; Gregory S. Girolami

    2016-01-01

    The title compound, tetrakis(dimethoxyboryl)methane (systematic name: octamethyl methanetetrayltetraboronate), C9H24B4O8 or C[B(OMe)2]4, is a useful synthetic intermediate. Crystals of this compound at 102 K conform to the orthorhombic space group Pbcn. The molecules, which reside on sites of crystallographic twofold symmetry, have idealized -4 point symmetry like most other CX4 molecules in which each X group bears two non-H substituents at the 1-position. The central C atom has a slightly d...

  16. Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

    Science.gov (United States)

    2015-07-21

    AFRL-OSR-VA-TR-2015-0195 CATALYSIS BY ATOMIC-SIZED CENTERS: METHANE ACTIVATION FOR PARTIAL OXIDATION AND COMBUSTION Horia Metiu UNIVERSITY OF...To) 01-04-2012 to 31-03-2015 4. TITLE AND SUBTITLE CATALYSIS BY ATOMIC-SIZED CENTERS: METHANE ACTIVATION FOR PARTIAL OXIDATION AND COMBUSTION 5a...livelink/llisapi.dll DISTRIBUTION A: Distribution approved for public release. Final Technical Report, FA9550-12-1-0147 “ CATALYSIS BY ATOMIC-SIZED

  17. Zeolites Modified Metal Cations as Catalysts in Hydrocarbon Oxidation and the Alkyl Alcohol

    Directory of Open Access Journals (Sweden)

    Agadadsh Makhmud Aliyev

    2014-09-01

    Full Text Available The results of studies on the creation of highly metalltceolitnyh systems and the study of their catalytic activities in the oxidation of lower olefin hydrocarbons (ethylene to acetaldehyde, acetone, propylene, butylene methyl ethyl ketone; aliphatic C1-C5 alcohols to their corresponding aldehydes, ketones, carboxylic acids and carboxylic acid esters; oxidative dehydrogenation of naphthenes in the alicyclic diene hydrocarbons and the oxidative dimerization of methane to acetylene. It has been established that the selectivity of these catalysts determined optimal combination of metal components with the acidity and the structure of the zeolite. Selected highly effective catalysts for the reactions studied. Based on the results of experimental studies of the kinetics of the reactions of oxidation of lower olefin hydrocarbons and aliphatic alcohols, the oxidative dehydrogenation of naphthenes and oxidative coupling of methane on the synthesized catalysts are represented by their probable stepwise mechanism and kinetic models developed reactions.

  18. Electrocatalytic methane dimerization with a Yb-doped SrCeO3 solid electrolyte

    International Nuclear Information System (INIS)

    Chiang, P.H.; Eng, D.; Stoukides, M.

    1991-01-01

    This paper reports on the electrocatalytic nonoxidative dimerization of methane to ethane and ethylene that was studied at 750 degrees C and 1 atm. The electrochemical cell used as Ag/SrCa 0.95 Yb 0.05 O 3 /Ag where the solid electrolyte was a proton conductor. By applying a current to the cell H + was pumped to or from the Ag electrodes. Under closed circuit the rate of methane dehydrogenation to ethane and ethylene could increase to as much as eight times the open-circuit rate. The electrolyte cell offers a promising advantage over conventional catalyst supports

  19. Experimental evaluation of methane dry reforming process on a membrane reactor to hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Fabiano S.A.; Benachour, Mohand; Abreu, Cesar A.M. [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. of Chemical Engineering], Email: f.aruda@yahoo.com.br

    2010-07-01

    In a fixed bed membrane reactor evaluations of methane-carbon dioxide reforming over a Ni/{gamma}- Al{sub 2}O{sub 3} catalyst were performed at 773 K, 823 K and 873 K. A to convert natural gas into syngas a fixed-bed reactor associate with a selective membrane was employed, where the operating procedures allowed to shift the chemical equilibrium of the reaction in the direction of the products of the process. Operations under hydrogen permeation, at 873 K, promoted the increase of methane conversion, circa 83%, and doubled the yield of hydrogen production, when compared with operations where no hydrogen permeation occurred. (author)

  20. Catalysts, methods of making catalysts, and methods of use

    KAUST Repository

    Renard, Laetitia

    2014-03-06

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  1. Potential for CO2 sequestration and enhanced coalbed methane production in the Netherlands

    OpenAIRE

    Hamelinck, C.N.; Schreurs, H.; Faaij, A.P.C.; Ruijg, G.J.; Jansen, Daan; Pagnier, H.; Bergen, F. van; Wolf, K.-H.; Barzandji, O.; Bruining, H.

    2006-01-01

    This study investigated the technical and economic feasibility of using CO2 for the enhanced production of coal bed methane (ECBM) in the Netherlands. This concept could lead to both CO2 storage by adsorbing CO2 in deep coal layers that are not suitable for mining, as well as production of methane. For every two molecules of CO2 injected, roughly one molecule of methane is produced. The work included an investigation of the potential CBM reserves in the Dutch underground and the related CO2 s...

  2. The effect of potassium addition to Pt supported on YSZ on steam reforming of mixtures of methane and ethane

    NARCIS (Netherlands)

    Graf, P.O.; Mojet, Barbara; Lefferts, Leonardus

    2009-01-01

    The influence of potassium addition on Pt supported on yttrium-stabilized zirconia (YSZ) was studied with FT-IR CO adsorption and CO-FT-IR-TPD, in order to understand the effect of potassium on the performance of the catalyst in reforming of mixtures of methane and ethane. Potassium modification of

  3. Effects of Mn- and K-addition on catalytic activity of calcium oxide for methane activation

    International Nuclear Information System (INIS)

    Park, Jong Sik; Kong, Jang Il; Lee, Sung Han; Jun, Jong Ho

    1998-01-01

    Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800 .deg. C to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction (XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally p(CH 4 )/p(O 2 )=250 Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best C 2 yield of 8.0% with a selectivity of 43.2% at 775 .deg. C. The C 2 selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO((Mn)>6.3 mol%)catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the C 2 selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000 .deg. C at Po2's of 10 -3 to 10 -1 atm. The electrical conductivity was decreased with Mn-doping and increased with increasing Po 2 in the range of 10 -3 to 10 -1 atm, indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry

  4. Catalyst in Basic Oleochemicals

    Directory of Open Access Journals (Sweden)

    Eva Suyenty

    2007-10-01

    Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

  5. Study of spent hydrorefining catalysts

    International Nuclear Information System (INIS)

    Gellerman, M.M.; Aliev, R.R.; Sidel'kovskaya, V.G.

    1993-01-01

    Aluminonickelmolybdenum catalysts for diesel fuel hydrorefining have been studied by DTA, XSPS, and diffuse reflection spectroscopy. Chemical and phase states of molybdenum compounds in samples of fresh catalyst, regenerated one after one year operation, and clogged with coke catalyst after five year operation, are determined. Chemical reactions and crystal-phase transformations of the molybdenum compounds during catalyst deactivation and regeneration are discussed

  6. Dynamic Chemical and Structural Changes of Heterogeneous Catalysts Observed in Real Time: From Catalysis-Induced Fluxionality to Catalytic Cycles

    Science.gov (United States)

    2014-11-26

    Changes of Heterogeneous Catalysts Observed in Real Time: From Catalysis -Induced Fluxionality to Catalytic Cycles” (FA9550-12-1-0204) Robert M. Rioux...report The results from “Dynamic Chemical and Structural Changes of Heterogeneous Catalysts Observed in Real Time: From Catalysis -Induced... fuels via the Fischer-Tropsch process. One reaction that is particularly detrimental to the Fischer-Tropsch process is the methanation of carbon

  7. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

    Abrams, B. L.; Vesborg, Peter Christian Kjærgaard

    2013-01-01

    on titania (V2O5-WO3/TiO2) as the example catalyst. The main photocatalysts examined for mineralization of organic compounds were TiO2 and MoS2. It is important to obtain insight into the catalyst structure-to-activity relationship in order to understand and locate the active site(s). In this chapter......The properties of catalysts used in environmental remediation are described here through specific examples in heterogeneous catalysis and photocatalysis. In the area of heterogeneous catalysis, selective catalytic reduction (SCR) of NOx was used as an example reaction with vanadia and tungsta...

  8. Methane production and methane consumption: a review of processes underlying wetland methane fluxes.

    NARCIS (Netherlands)

    Segers, R.

    1998-01-01

    Potential rates of both methane production and methane consumption vary over three orders of magnitude and their distribution is skew. These rates are weakly correlated with ecosystem type, incubation temperature, in situ aeration, latitude, depth and distance to oxic/anoxic interface. Anaerobic

  9. Partial oxidation of methane over bimetallic copper- and nickel-actinide oxides (Th, U)

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Ana C.; Goncalves, A.P.; Gasche, T. Almeida [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal); Ferraria, A.M.; Rego, A.M. Botelho do [Universidade Tecnica de Lisboa, IST, Centro de Quimica-Fisica Molecular and IN, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Correia, M.R.; Bola, A. Margarida [I3N-Universidade de Aveiro, Department Fisica, Aveiro (Portugal); Branco, J.B., E-mail: jbranco@itn.p [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal)

    2010-05-14

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi{sub 2} (An = Th, U) and ThCu{sub 2} were used as precursors and the products (2NiO.UO{sub 3}, 2NiO.ThO{sub 2} and 2CuO.ThO{sub 2}) characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and temperature-programmed reduction. The catalysts were active and selective for the conversion of methane to H{sub 2} and CO and stable for a period of time of {approx}18 h on stream. The nickel catalysts were more active and selective than the copper catalyst and, under the same conditions, show a catalytic behaviour comparable to that of a platinum commercial catalyst, 5 wt% Pt/Al{sub 2}O{sub 3}. The catalytic activity increases when uranium replaces thorium and the selectivity of this type of materials is clearly different from that of single metal oxides and/or mechanical mixtures. The good catalytic behaviour of the bimetallic copper- and nickel-actinide oxides was attributed to an unusual interaction between copper or nickel oxide and the actinide oxide phase as showed by H{sub 2}-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  10. Exceptional activity for methane combustion over modular Pd@CeO2 subunits on functionalized Al2O3.

    Science.gov (United States)

    Cargnello, M; Delgado Jaén, J J; Hernández Garrido, J C; Bakhmutsky, K; Montini, T; Calvino Gámez, J J; Gorte, R J; Fornasiero, P

    2012-08-10

    There is a critical need for improved methane-oxidation catalysts to both reduce emissions of methane, a greenhouse gas, and improve the performance of gas turbines. However, materials that are currently available either have low activity below 400°C or are unstable at higher temperatures. Here, we describe a supramolecular approach in which single units composed of a palladium (Pd) core and a ceria (CeO(2)) shell are preorganized in solution and then homogeneously deposited onto a modified hydrophobic alumina. Electron microscopy and other structural methods revealed that the Pd cores remained isolated even after heating the catalyst to 850°C. Enhanced metal-support interactions led to exceptionally high methane oxidation, with complete conversion below 400°C and outstanding thermal stability under demanding conditions.

  11. CH4 reforming with CO2 for syngas production over nickel catalysts supported on mesoporous nanostructured γ-Al2O3

    International Nuclear Information System (INIS)

    Majidian, Nasrollah; Habibi, Narges; Rezaei, Mehran

    2014-01-01

    Nanostructured γ-Al 2 O 3 with high surface area and mesoporous structure was synthesized by sol-gel method and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by XRD, BET, TPR, TPH, SEM and TPO techniques. The BET analysis showed a high surface area of 204m 2 g -1 and a narrow pore-size distribution centered at a diameter of 5.5 nm for catalyst support. The results revealed that an increase in nickel loading from 5 to 15 wt% decreased the surface area of catalyst from 182 to 160 m 2 g -1 . In addition, the catalytic results showed an increase in methane conversion with increase in nickel content. TPO analysis revealed that the coke deposition increased with increasing in nickel loading, and the catalyst with 15 wt% of nickel showed the highest degree of carbon formation. SEM and TPH analyses confirmed the formation of whisker type carbon over the spent catalysts. Increasing CO 2 /CH 4 ratio increased the methane conversion. The BET analysis of spent catalysts indicated that the mesoporous structure of catalysts still remained after reaction

  12. Catalyst for microelectromechanical systems microreactors

    Science.gov (United States)

    Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

    2010-06-29

    A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

  13. Epoxidation catalyst and process

    Science.gov (United States)

    Linic, Suljo; Christopher, Phillip

    2010-10-26

    Disclosed herein is a catalytic method of converting alkenes to epoxides. This method generally includes reacting alkenes with oxygen in the presence of a specific silver catalyst under conditions suitable to produce a yield of the epoxides. The specific silver catalyst is a silver nanocrystal having a plurality of surface planes, a substantial portion of which is defined by Miller indices of (100). The reaction is performed by charging a suitable reactor with this silver catalyst and then feeding the reactants to the reactor under conditions to carry out the reaction. The reaction may be performed in batch, or as a continuous process that employs a recycle of any unreacted alkenes. The specific silver catalyst has unexpectedly high selectivity for epoxide products. Consequently, this general method (and its various embodiments) will result in extraordinarily high epoxide yields heretofore unattainable.

  14. 77 FR 40032 - Methane Hydrate Advisory Committee

    Science.gov (United States)

    2012-07-06

    ... DEPARTMENT OF ENERGY Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of methane...

  15. Reducing uncertainty in methane emission estimates from permafrost peatlands

    Science.gov (United States)

    Christensen, Torben R.

    2016-04-01

    Reducing uncertainty in methane emission estimates from permafrost peatlands Torben R. Christensen1,2 and coworkers 1) Department of Physical Geography and Ecosystem Science, Lund University, Sweden 2) Arctic Research Centre, Aarhus University, Denmark Depending on factors including temperature, snow duration and soil moisture conditions, emissions of the greenhouse gas methane from permafrost peatlands can vary by factors of 2-4 between years. This variability is clear in atmospheric measurements of the gas, but a lack of ground-based data is making it hard to locate the methane sources responsible. Methane monitoring in the Arctic is expensive, requiring sophisticated analysis equipment such as power requiring laser spectrometer analysis made in remote places. This also puts demands on the logistics where infrastructures and field stations that offer line-power in the field are in high demand but very rarely found. Research projects therefore typically focus on one site, and run for a year or two. Longer term monitoring programs, which document climate, hydrology, phenology and population dynamics of birds and mammals, rarely include carbon fluxes since it is technically challenging to measure. One that does is the Greenland Ecosystem Monitoring program that started at the Zackenberg research station, which has recorded substantial methane flux variations for almost a decade in North-east Greenland. Such multi-year studies show that, while there is some connection between the amounts of methane released from one year to the next, accurate forecasting is difficult. They also highlight the importance of extending monitoring beyond the growing period into the frozen season, both in spring and autumn. A spatially distributed network of long-term monitoring stations in the Arctic, with consistency between measurements, is badly needed to improve this situation. Productive methane 'hot spots', many sporadic, have also been identified in recent studies. By ventilating

  16. Latent olefin metathesis catalysts

    OpenAIRE

    Monsaert, Stijn; Lozano Vila, Ana; Drozdzak, Renata; Van Der Voort, Pascal; Verpoort, Francis

    2009-01-01

    Olefin metathesis is a versatile synthetic tool for the redistribution of alkylidene fragments at carbon-carbon double bonds. This field, and more specifically the development of task-specific, latent catalysts, attracts emerging industrial and academic interest. This tutorial review aims to provide the reader with a concise overview of early breakthroughs and recent key developments in the endeavor to develop latent olefin metathesis catalysts, and to illustrate their use by prominent exampl...

  17. Plasmatron-catalyst system

    Science.gov (United States)

    Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

    2007-10-09

    A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

  18. Methanation of CO2 over Zeolite-Encapsulated Nickel Nanoparticles

    DEFF Research Database (Denmark)

    Goodarzi, Farnoosh; Kang, Liqun; Wang, Feng Ryan

    2018-01-01

    Efficient methanation of CO2 relies on the development of more selective and stable heterogeneous catalysts. Here we present a simple and effective method to encapsulate Ni nanoparticles in zeolite silicalite-1. In this method, the zeolite is modified by selective desilication, which creates intr...... Ni h-1. The encapsulated Ni nanoparticles show no change in activity or selectivity after 50 h of operation, although post-catalysis characteri-sation reveals some particle migration.......Efficient methanation of CO2 relies on the development of more selective and stable heterogeneous catalysts. Here we present a simple and effective method to encapsulate Ni nanoparticles in zeolite silicalite-1. In this method, the zeolite is modified by selective desilication, which creates intra......-particle voids and mesopores that facilitate the formation of small and well-dispersed nanoparticles upon impregnation and reduction. TEM and XPS analysis confirm that a significant part of the Ni nanoparticles are situated inside the zeolite rather than on the outer surface. The encapsulation results...

  19. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    Science.gov (United States)

    Angelici, Robert J.; Gao, Hanrong

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

  20. Phytoremediation of Atmospheric Methane

    Science.gov (United States)

    2013-04-15

    greenhouse gases produced by human activity are  carbon   dioxide , methane and  nitrous oxide.  Much attention has been directed toward CO2 mitigation...surface  ocean .   Acidification  and ultimately warming due to CO2 alone must be  addressed by removing CO2 from the atmosphere and prevention of further...as a  carbon  and energy source. One soluble MMO (sMMO)  system is expressed by some methanotrophs under conditions of low copper concentration and

  1. Selective Coke Combustion by Oxygen Pulsing During Mo/ZSM-5-Catalyzed Methane Dehydroaromatization.

    Science.gov (United States)

    Kosinov, Nikolay; Coumans, Ferdy J A G; Uslamin, Evgeny; Kapteijn, Freek; Hensen, Emiel J M

    2016-11-21

    Non-oxidative methane dehydroaromatization is a promising reaction to directly convert natural gas into aromatic hydrocarbons and hydrogen. Commercialization of this technology is hampered by rapid catalyst deactivation because of coking. A novel approach is presented involving selective oxidation of coke during methane dehydroaromatization at 700 °C. Periodic pulsing of oxygen into the methane feed results in substantially higher cumulative product yield with synthesis gas; a H 2 /CO ratio close to two is the main side-product of coke combustion. Using 13 C isotope labeling of methane it is demonstrated that oxygen predominantly reacts with molybdenum carbide species. The resulting molybdenum oxides catalyze coke oxidation. Less than one-fifth of the available oxygen reacts with gaseous methane. Combined with periodic regeneration at 550 °C, this strategy is a significant step forward, towards a process for converting methane into liquid hydrocarbons. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  2. Recent advances in methane activation

    Energy Technology Data Exchange (ETDEWEB)

    Huuska, M.; Kataja, K. [VTT Chemical Technology, Espoo (Finland)

    1996-12-31

    Considerable work has been done in the research and development of methane conversion technologies. Although some promising conversion processes have been demonstrated, further advances in engineering and also in the chemistry are needed before these technologies become commercial. High-temperature processes, e.g. the oxidative coupling of methane, studied thoroughly during the last 15 years, suffer from severe theoretical yield limits and poor economics. In the long term, the most promising approaches seem to be the organometallic and, especially, the biomimetic activation of methane. (author) (22 refs.)

  3. Methane hydroxylation: a biomimetic approach

    International Nuclear Information System (INIS)

    Shilov, Aleksandr E; Shteinman, Al'bert A

    2012-01-01

    The review addresses direct methane oxidation — an important fundamental problem, which has attracted much attention of researchers in recent years. Analysis of the available results on biomimetic and bio-inspired methane oxygenation has demonstrated that assimilating of the experience of Nature on oxidation of methane and other alkanes significantly enriches the arsenal of chemistry and can radically change the character of the entire chemical production, as well as enables the solution of many material, energetic and environmental problems. The bibliography includes 310 references.

  4. Anthropogenic methane ebullition and continuous flux measurement

    Science.gov (United States)

    Alshboul, Zeyad

    2017-04-01

    Keywords: Methane, Wastewater, Effluent, Anaerobic treatment. Municipal wastewater treatment plants (WWTPs) have shown to emit significant amount of methane during treatment processes. While most of studies cover only in-plant diffusive methane flux, magnitude and sources of methane ebullition have not well assessed. Moreover, the reported results of methane emissions from WWTPs are based on low spatial and temporal resolution. Using a continuous measurement approach of methane flux rate for effluent system and secondary clarifier treatment process at one WWTP in Southwest Germany, our results show that high percentage of methane is emitted by ebullition during the anaerobic treatment (clarification pond) with high spatial and temporal variability. Our measurements revealed that no ebullition is occur at the effluent system. The observed high contribution of methane ebullition to the total in-plant methane emission, emphasizes the need for considering in-plant methane emission by ebullition as well as the spatial and temporal variability of these emissions.

  5. The effect of precipitants on Ni-Al2O3 catalysts prepared by a co-precipitation method for internal reforming in molten carbonate fuel cells

    Science.gov (United States)

    Jung, You-Shick; Yoon, Wang-Lai; Seo, Yong-Seog; Rhee, Young-Woo

    2012-01-01

    Ni-Al2O3 catalysts are prepared via the co-precipitation method using various precipitants: urea, Na2CO3, NaOH, K2CO3, KOH and NH4OH. The effects of the precipitants on the physicochemical properties and catalytic activities of the Ni-Al2O3 catalysts are investigated. The Ni50-urea catalyst displays the largest specific surface area and the highest pore volume. This catalyst also exhibits the highest Ni dispersion and the largest Ni surface area. Ni50-urea catalyst prepared with urea as precipitant and Ni50-K2CO3 catalyst prepared with K2CO3 as precipitant exhibit high pore volumes and good catalytic activities for methane steam reforming. The Ni50-urea catalyst exhibits the best physicochemical properties and shows good catalytic activity and a strong resistance to electrolyte contamination. PMID:22962548

  6. A Novel Slurry-Based Biomass Reforming Process Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Emerson, Sean C. [United Technologies Research Center, East Hartford, CT (United States); Davis, Timothy D. [United Technologies Research Center, East Hartford, CT (United States); Peles, A. [United Technologies Research Center, East Hartford, CT (United States); She, Ying [United Technologies Research Center, East Hartford, CT (United States); Sheffel, Joshua [United Technologies Research Center, East Hartford, CT (United States); Willigan, Rhonda R. [United Technologies Research Center, East Hartford, CT (United States); Vanderspurt, Thomas H. [United Technologies Research Center, East Hartford, CT (United States); Zhu, Tianli [United Technologies Research Center, East Hartford, CT (United States)

    2011-09-30

    to hydrogen, methane, and carbon dioxide was repeatedly demonstrated in batch reactors varying in size from 50 mL to 7.6 L. The different wood sources (e.g., swamp maple, poplar, and commercial wood flour) were converted in the presence of a heterogeneous catalyst and base at relatively low temperatures (e.g., 310°C) at sub-critical pressures sufficient to maintain the liquid phase. Both precious metal and base metal catalysts were found to be active for the liquid phase hydrolysis and reforming of wood. Pt-based catalysts, particularly Pt-Re, were shown to be more selective toward breaking C-C bonds, resulting in a higher selectivity to hydrogen versus methane. Ni-based catalysts were found to prefer breaking C-O bonds, favoring the production of methane. The project showed that increasing the concentration of base (base to wood ratio) in the presence of Raney Ni catalysts resulted in greater selectivity toward hydrogen but at the expense of increasing the production of undesirable organic acids from the wood, lowering the amount of wood converted to gas. It was shown that by modifying Ni-based catalysts with dopants, it was possible to reduce the base concentration while maintaining the selectivity toward hydrogen and increasing wood conversion to gas versus organic acids. The final stage of the project was the construction and testing of a demonstration unit for H2 production. This continuous flow demonstration unit consisted of wood slurry and potassium carbonate feed pump systems, two reactors for hydrolysis and reforming, and a gas-liquid separation system. The technical challenges associated with unreacted wood fines and Raney Ni catalyst retention limited the demonstration unit to using a fixed bed Raney Ni catalyst form. The lower activity of the larger particle Raney Ni in turn limited the residence time and thus the wood mass flow feed rate to 50 g min-1 for a 1 wt% wood slurry. The project demonstrated continuous H2 yields with unmodified, fixed bed

  7. Global Methane Biogeochemistry

    Science.gov (United States)

    Reeburgh, W. S.

    2003-12-01

    Methane (CH4) has been studied as an atmospheric constituent for over 200 years. A 1776 letter from Alessandro Volta to Father Campi described the first experiments on flammable "air" released by shallow sediments in Lake Maggiore (Wolfe, 1996; King, 1992). The first quantitative measurements of CH4, both involving combustion and gravimetric determination of trapped oxidation products, were reported in French by Boussingault and Boussingault, 1864 and Gautier (1901), who reported CH4 concentrations of 10 ppmv and 0.28 ppmv (seashore) and 95 ppmv (Paris), respectively. The first modern measurements of atmospheric CH4 were the infrared absorption measurements of Migeotte (1948), who estimated an atmospheric concentration of 2.0 ppmv. Development of gas chromatography and the flame ionization detector in the 1950s led to observations of vertical CH4 distributions in the troposphere and stratosphere, and to establishment of time-series sampling programs in the late 1970s. Results from these sampling programs led to suggestions that the concentration of CH4, as that of CO2, was increasing in the atmosphere. The possible role of CH4 as a greenhouse gas stimulated further research on CH4 sources and sinks. Methane has also been of interest to microbiologists, but findings from microbiology have entered the larger context of the global CH4 budget only recently.Methane is the most abundant hydrocarbon in the atmosphere. It plays important roles in atmospheric chemistry and the radiative balance of the Earth. Stratospheric oxidation of CH4 provides a means of introducing water vapor above the tropopause. Methane reacts with atomic chlorine in the stratosphere, forming HCl, a reservoir species for chlorine. Some 90% of the CH4 entering the atmosphere is oxidized through reactions initiated by the OH radical. These reactions are discussed in more detail by Wofsy (1976) and Cicerone and Oremland (1988), and are important in controlling the oxidation state of the atmosphere

  8. Promoting Effect of CeO2 Addition on Activity and Catalytic Stability in Steam Reforming of Methane over Ni/Al2O3

    International Nuclear Information System (INIS)

    Rakib, A.; Gennequin, C.; Ringot, S.; Aboukais, A.; Abi-Aad, E.; Dhainaut, T.

    2011-01-01

    Hydrogen production by steam reforming of methane was studied over Ni catalysts supported on CeO 2 , Al 2 O 3 and CeO 2 -Al 2 O 3 . These catalysts were prepared using the impregnation method and characterized by XRD. The effect of CeO2 promoter on the catalytic performance of Ni/Al 2 O 3 catalyst for methane steam reforming reaction was investigated. In fact, CeO 2 had a positive effect on the catalytic activity in this reaction. Experimental results demonstrated that Ni/CeO 2 -Al 2 O 3 catalyst showed excellent catalytic activity and high reaction performance. In addition, the effects of reaction temperature and metal content on the conversion of CH 4 and H 2 /CO ratio were also investigated. Results indicated that CH4 conversion increased significantly with the increase of the reaction temperature and metal content. (author)

  9. Cerium Modified Pillared Montmorillonite Supported Cobalt Catalysts for Fischer Tropsch Synthesis

    International Nuclear Information System (INIS)

    Ahmad, N.; Ali, Z.; Abbas, S. M.; Hussain, F.

    2015-01-01

    Fischer-Tropsch (FT) synthesis was accomplished over Al-pillared Montmorillonite supported 20 wt% Co modified with different weight% of cerium catalysts. These catalysts were prepared by impregnation method while structural characterizations of the prepared samples were performed by XRD, TPR, NH/sub 3/TPD, TGA, BET, XRF and SEM techniques. The Fischer Tropsch reaction was studied in fixed bed micro catalytic reactor at temperature range of 220, 260 and 275 degree C and at different pressure (1, 5 and 10 bars). From the activity results, it was found that by pillaring NaMMT with Al higher catalytic activity and lower methane selectivity of NaMMT was achieved. Furthermore, the results of FT synthesis reaction revealed that cerium incorporation increased the dispersion of Co/sub 3/O/sub 4/ on the surface and consequently resulted in enhanced catalytic activity. Additionally, the C/sub 5/-C/sub 12/ hydrocarbons and methane selectivity increased while C/sub 22+/ hydrocarbons selectivity was decreased over cerium modified catalysts. Higher reaction temperature (>220 degree C) resulted in significant enhancement in CO conversion and methane selectivity. Though, increase in pressure from 1 to 10 bars eventually resulted in increase in C/sub 5+/ hydrocarbons and decrease in methane and C/sub 2/-C/sub 5/ hydrocarbons selectivity. (author)

  10. Facile Synthesis of Bis(indolyl)methanes Catalyzed by α-Chymotrypsin

    OpenAIRE

    Xie, Zong-Bo; Sun, Da-Zhao; Jiang, Guo-Fang; Le, Zhang-Gao

    2014-01-01

    A mild and efficient method catalyzed by α-chymotrypsin was developed for the synthesis of bis(indolyl)methanes through a cascade process between indole and aromatic aldehydes. In the ethanol aqueous solution, a green medium, a wide range of aromatic aldehydes could react with indole to afford the desired products with moderate to good yields (from 68% to 95%) using a little α-chymotrypsin as catalyst.

  11. Facile synthesis of bis(indolyl)methanes catalyzed by α-chymotrypsin.

    Science.gov (United States)

    Xie, Zong-Bo; Sun, Da-Zhao; Jiang, Guo-Fang; Le, Zhang-Gao

    2014-11-27

    A mild and efficient method catalyzed by α-chymotrypsin was developed for the synthesis of bis(indolyl)methanes through a cascade process between indole and aromatic aldehydes. In the ethanol aqueous solution, a green medium, a wide range of aromatic aldehydes could react with indole to afford the desired products with moderate to good yields (from 68% to 95%) using a little α-chymotrypsin as catalyst.

  12. Tritium transfer process using the CRNL wetproof catalyst

    International Nuclear Information System (INIS)

    Chuang, K.T.; Holtslander, W.J.

    1980-01-01

    The recovery of tritium from heavy water in CANDU reactor systems requires the transfer of the tritium atoms from water to hydrogen molecules prior to tritium concentration by cryogenic distillation. Isotopic exchange between liquid water and hydrogen using the CRNL-developed wetproof catalyst provides an effective method for the tritium transfer process. The development of this process has required the translation of the technology from a laboratory demonstration of catalyst activity for the exchange reaction to proving and demonstration that the process will meet the practical restraints in a full-scale tritium recovery plant. This has led to a program to demonstrate acceptable performance of the catalyst at operating conditions that will provide data for design of large plants. Laboratory and pilot plant work has shown adequate catalyst lifetimes, demonstrated catalyst regeneration techniques and defined and required feedwater purification systems to ensure optimum catalyst performance. The ability of the catalyst to promote the exchange of hydrogen isotopes between water and hydrogen has been shown to be technically feasible for the tritium transfer process

  13. Magnetic and dendritic catalysts.

    Science.gov (United States)

    Wang, Dong; Deraedt, Christophe; Ruiz, Jaime; Astruc, Didier

    2015-07-21

    The recovery and reuse of catalysts is a major challenge in the development of sustainable chemical processes. Two methods at the frontier between homogeneous and heterogeneous catalysis have recently emerged for addressing this problem: loading the catalyst onto a dendrimer or onto a magnetic nanoparticle. In this Account, we describe representative examples of these two methods, primarily from our research group, and compare them. We then describe new chemistry that combines the benefits of these two methods of catalysis. Classic dendritic catalysis has involved either attaching the catalyst covalently at the branch termini or within the dendrimer core. We have used chelating pyridyltriazole ligands to insolubilize catalysts at the termini of dendrimers, providing an efficient, recyclable heterogeneous catalysts. With the addition of dendritic unimolecular micelles olefin metathesis reactions catalyzed by commercial Grubbs-type ruthenium-benzylidene complexes in water required unusually low amounts of catalyst. When such dendritic micelles include intradendritic ligands, both the micellar effect and ligand acceleration promote faster catalysis in water. With these types of catalysts, we could carry out azide alkyne cycloaddition ("click") chemistry with only ppm amounts of CuSO4·5H2O and sodium ascorbate under ambient conditions. Alternatively we can attach catalysts to the surface of superparamagnetic iron oxide nanoparticles (SPIONs), essentially magnetite (Fe3O4) or maghemite (γ-Fe2O3), offering the opportunity to recover the catalysts using magnets. Taking advantage of the merits of both of these strategies, we and others have developed a new generation of recyclable catalysts: dendritic magnetically recoverable catalysts. In particular, some of our catalysts with a γ-Fe2O3@SiO2 core and 1,2,3-triazole tethers and loaded with Pd nanoparticles generate strong positive dendritic effects with respect to ligand loading, catalyst loading, catalytic activity and

  14. Enteric Methane Emission from Pigs

    DEFF Research Database (Denmark)

    Jørgensen, Henry; Theil, Peter Kappel; Knudsen, Knud Erik Bach

    2011-01-01

    per kg meat produced is increased (Fernández et al. 1983; Lekule et al. 1990). The present chapter will summarise our current knowledge concerning dietary and enteric fermentation that may influence the methane (CH4) emission in pigs. Enteric fermentation is the digestive process by which.......3 % of the worlds pig population. The main number of pigs is in Asia (59.6 %) where the main pig population stay in China (47.8 % of the worlds pig population). The objective of the chapter is therefore: To obtain a general overview of the pigs’ contribution to methane emission. Where is the pigs’ enteric gas...... produced and how is it measured. The variation in methane emission and factors affecting the emission. Possibility for reducing the enteric methane emission and the consequences....

  15. Methane Liquid Level Sensor Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Advanced Technologies Group, Inc. proposes the development of a Methane Liquid-Level Sensor, (MLS) for In-Space cryogenic storage capable of continuous monitoring of...

  16. Methane LIDAR Laser Technology Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Fibertek proposes to develop laser technology intended to meet NASA's need for innovative lidar technologies for atmospheric measurements of methane. NASA and the...

  17. Miniature Airborne Methane Sensor Project

    Data.gov (United States)

    National Aeronautics and Space Administration — KalScott Engineering, and the subcontractor, Princeton University propose the development and demonstration of compact and robust methane sensor for small Unmanned...

  18. Development of Sulfur and Carbon Tolerant Reforming Alloy Catalysts Aided by Fundamental Atomistics Insights

    Energy Technology Data Exchange (ETDEWEB)

    Suljo Linic

    2006-08-31

    Current hydrocarbon reforming catalysts suffer from rapid carbon and sulfur poisoning. Even though there is a tremendous incentive to develop more efficient catalysts, these materials are currently formulated using inefficient trial and error experimental approaches. We have utilized a novel hybrid experimental/theoretical approach, combining quantum Density Functional Theory (DFT) calculations and various state-of-the-art experimental tools, to formulate carbon tolerant reforming catalysts. We have employed DFT calculations to develop molecular insights into the elementary chemical transformations that lead to carbon poisoning of Ni catalysts. Based on the obtained molecular insights, we have identified, using DFT quantum calculation, Sn/Ni alloy as a potential carbon tolerant reforming catalyst. Sn/Ni alloy was synthesized and tested in steam reforming of methane, propane, and isooctane. We demonstrated that the alloy catalyst is carbon-tolerant under nearly stoichiometric steam-to-carbon ratios. Under these conditions, monometallic Ni is rapidly poisoned by sp2 carbon deposits. The research approach is distinguished by a few characteristics: (a) Knowledge-based, bottom-up approach, compared to the traditional trial and error approach, allows for a more efficient and systematic discovery of improved catalysts. (b) The focus is on exploring alloy materials which have been largely unexplored as potential reforming catalysts.

  19. Device for manufacturing methane or synthetic gas from materials containing carbon using a nuclear reactor

    International Nuclear Information System (INIS)

    Jaeger, W.

    1984-01-01

    This invention concerns a device for manufacturing methane or synthetic gas from materials containing carbon using a nuclear reactor, where part of the carbon is gasified with hydration and the remaining carbon is converted to synthetic gas by adding steam. This synthetic gas consists mainly of H 2 , CO, CO 2 and CH 4 and can be converted to methane in so-called methanising using a nickel catalyst. The hydrogen gasifier is situated in the first of two helium circuits of a high temperature reactor, and the splitting furnace is situated in the second helium circuit, where part of the methane produced is split into hydrogen at high temperature, which is used for the hydrating splitting of another part of the material containing carbon. (orig./RB) [de

  20. Toward an understanding of methane selectivity in the Fischer-Tropsch process

    Science.gov (United States)

    Psarras, Peter C.

    The purpose of this research is to elucidate a better understanding of the conditions relevant to methane selectivity in the Fischer-Tropsch (FT) process. The development of more efficient FT catalysts can result in great commercial profit. The industrially relevant FT process has long been hampered by the production of methane. Nearly 60 percent of FT capital is devoted to the removal of methane and purification of feed-stock gases through steam-reforming. Naturally, a more efficient FT catalyst would need to have a reasonable balance between catalytic activity and suppression of methane formation (low methane selectivity). Though a significant amount of work has been devoted to understanding the mechanisms involved in methane selectivity, the exact mechanism is still not well understood. Density functional theory (DFT) methods provide an opportunity to explore the FT catalytic process at the molecular level. This work represents a combination of various DFT approaches in an attempt to gather new insight on the conditions relevant to methane selectivity. A thorough understanding of the electronic environment involved in the surface-adsorbate interaction is necessary to the advancement of more efficient Fischer-Tropsch catalysts. This study investigates the promotive effect of four late transition metals (Cu, Ag, Au and Pd) on three FT catalytic surfaces (Fe, Co and Ni). The purpose of this research is to examine the surface-adsorbate interaction from two perspectives: 1) interactions occurring between FT precursors and small, bimetallic surface analogs (clusters), and 2) plane-wave calculations of the interactions between FT precursors and simulated bulk surfaces. Our results suggest that promising candidates for the reduction of FT methane selectivity include Au and Pd on Ni, Au and Ag on Co, and Cu, Ag, and Pd on Fe. Additionally, cluster models were susceptible to effects not encountered in the plane-wave approach. Thermodynamic trends can be made more