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.

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.

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.

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

KAUST Repository

Zhou, Lu; Guo, Y.; Basset, Jean-Marie; Kameyama, H.

2015-01-01

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.

Assessing the techno-environmental performance of CO2 utilization via dry reforming of methane for the production of dimethyl ether

NARCIS (Netherlands)

Schakel, Wouter|info:eu-repo/dai/nl/369280784; Oreggioni, Gabriel; Singh, Bhawna; Strømman, Anders; Ramírez, Andrea|info:eu-repo/dai/nl/284852414

2016-01-01

Abstract CO2 utilization is gaining attention as a greenhouse gas abatement strategy complementary to CO2 storage. This study explores the techno-environmental performance of CO2 utilization trough dry reforming of methane into syngas for the production of dimethyl ether (DME). The CO2 source is a

Thermodynamic analysis on the CO2 conversion processes of methane dry reforming for hydrogen production and CO2 hydrogenation to dimethyl ether

Science.gov (United States)

He, Xinyi; Liu, Liping

2017-12-01

Based on the principle of Gibbs free energy minimization, the thermodynamic analysis on the CO2 conversion processes of dry reforming of methane for H2 and CO2 hydrogenation to dimethyl ether was carried out. The composition of the reaction system was determined on the basis of reaction mechanism. The effects of reaction temperature, pressure and raw material composition on the equilibrium conversion and the selectivity of products were analyzed. The results show that high temperature, low pressure, CO2/CH4 molar ratio of 1.0-1.5 and appropriate amount of oxygen are beneficial to the dry reforming of methane. For CO2 hydrogenation to dimethyl ether, low temperature, high pressure, the appropriate H2/CO2 and the proper CO addition in feed are favorable. The calculated results are compared with the relevant studies, indicating that industrial catalytic technology needs further improvement.

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

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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.

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.

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)

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.

Solid oxide fuel cell technology coupled with methane dry reforming: A viable option for high efficiency plant with reduced CO2 emissions

International Nuclear Information System (INIS)

Barelli, L.; Ottaviano, A.

2014-01-01

Nowadays the control of greenhouse gas is probably the most challenging environmental policy issue. Since CO 2 is considered the major greenhouse gas (GHG) that contributes to the global warming, enforcing technological strategies aiming to avoid or reuse CO 2 emissions becomes crucial, in order to mitigate GHG environmental impact. Currently, solutions conventionally adopted to this purpose are carbon capture and storage (CCS) technologies. In this context, instead, the followed strategy aims to further improvements in energetic conversion efficiency with related reduced specific CO 2 emissions (per produced kWh e ). Therefore, with particular reference to the electric power generation, this paper proposes an innovative energy conversion system, based on solid oxide fuel cell (SOFC), characterized by higher efficiency and reduced CO 2 emission factor respect to an analogous conventional energy plant. In particular, the innovative solution consists of combining SOFC to methane dry reforming technology, while the conventional system refers to steam methane reforming-SOFC coupling. The innovative system performance up to 65% electric efficiency as cited in the paper, was validated through simulations carried out in Aspen Plus environment. - Highlights: • An innovative high efficiency plant with low CO 2 emissions is presented. • The new solution combined SOFC to methane dry reforming technology (CDR–SOFC). • A comparison between CDR–SOFC and SMR–SOFC system was carried out in Aspen Plus. • CDR–SOFC efficiency is greater of 6.4% percentage points respect to SMR–SOFC. • A CO 2 emission factor reduction of about 10% was achieved by CDR–SOFC plant

The Role of Neodymium in the Optimization of a Ni/CeO2 and Ni/CeZrO2 Methane Dry Reforming Catalyst

Directory of Open Access Journals (Sweden)

Alfonsina Pappacena

2018-04-01

Full Text Available The development of a sustainable economy based on the use of renewable resources and the reduction of greenhouse gases emissions is an important mandate in modern societies to minimize the global warming. The CO2-reforming of methane through a conversion of CO2 and CH4 to syngas is a suitable process for this purpose and there is growing interest in the development of new catalysts for this process’ application at an industrial scale. This study is the first to investigate methane dry reforming activity of nickel supported on CeO2 and CeO2–ZrO2 solid solutions doped with neodymium. The supports were synthesized using a surfactant-assisted co-precipitation method and characterized through several analytical techniques to understand the role of synthesis parameters in the distribution of the dopant as well as in the properties of the supports. Co-doping with Zr and Nd resulted in an enhancement of dry reforming activity of ceria due to a higher dispersion of Ni and changes in the strength of basic sites. It was also shown that the addition of Nd helped to mitigate coking issues by increasing the mobility of surface oxygen in ceria and ceria–zirconia oxides and, accordingly, the rate of oxidation of carbonaceous deposits.

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

KAUST Repository

Alotaibi, Raja; Alenazey, Feraih; Alotaibi, Faisal; Wei, Nini; Al-Fatesh, Ahmed; Fakeeha, Anis

2015-01-01

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.

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.

Solar hydrogen production: renewable hydrogen production by dry fuel reforming

Science.gov (United States)

Bakos, Jamie; Miyamoto, Henry K.

2006-09-01

SHEC LABS - Solar Hydrogen Energy Corporation constructed a pilot-plant to demonstrate a Dry Fuel Reforming (DFR) system that is heated primarily by sunlight focusing-mirrors. The pilot-plant consists of: 1) a solar mirror array and solar concentrator and shutter system; and 2) two thermo-catalytic reactors to convert Methane, Carbon Dioxide, and Water into Hydrogen. Results from the pilot study show that solar Hydrogen generation is feasible and cost-competitive with traditional Hydrogen production. More than 95% of Hydrogen commercially produced today is by the Steam Methane Reformation (SMR) of natural gas, a process that liberates Carbon Dioxide to the atmosphere. The SMR process provides a net energy loss of 30 to 35% when converting from Methane to Hydrogen. Solar Hydrogen production provides a 14% net energy gain when converting Methane into Hydrogen since the energy used to drive the process is from the sun. The environmental benefits of generating Hydrogen using renewable energy include significant greenhouse gas and criteria air contaminant reductions.

Hydrogen production from methane reforming: thermodynamic assessment

Energy Technology Data Exchange (ETDEWEB)

Assis, A.J.; Hori, Carla E.; Avila Neto, Cicero; Franco, Tatiana [Federal University of Uberlandia (UFU), MG (Brazil). School of Chemical Engineering]. E-mail: adilsonjassis@gmail.com

2008-07-01

The main contributions of this study are to conduct a comparative thermodynamic analysis of methane reforming reactions and to asses the influence of key operational variables on chemical equilibrium using an in-house code, developed in the open-source software Scilab{sup c} INRIA-ENPC (www.scilab.org). Equilibrium compositions are calculated by two distinct methods: evaluation of equilibrium constants and Lagrange multipliers. Both methods result in systems of non-linear algebraic equations, solved numerically using the Scilab function 'fsolve'. Comparison between experimental and simulated equilibrium data, published in the literature, was used to validate the simulated results. Effects of temperature, pressure, initial H{sub 2}O/CH{sub 4} ratio (steam reforming), initial CH{sub 4}:CO{sub 2}:N{sub 2} ratio (dry reforming) and initial O{sub 2}/CH{sub 4} ratio (partial oxidation) on the reaction products were evaluated. (author)

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.

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....... The methane steam reforming reaction cannot be modeled without taking CO and H coverages into account. This is especially important at low temperatures and higher partial pressures of CO and H-2. For methane CO2 reforming experiments, it is also necessary to consider the repulsive interaction of CO...

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.

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

A Short Review on the Catalytic Activity of Hydrotalcite-Derived Materials for Dry Reforming of Methane

Directory of Open Access Journals (Sweden)

Radosław Dębek

2017-01-01

Full Text Available Nickel-containing hydrotalcite-derived materials have been recently proposed as promising materials for methane dry reforming (DRM. Based on a literature review and on the experience of the authors, this review focuses on presenting past and recent achievements on increasing activity and stability of hydrotalcite-based materials for DRM. The use of different NiMgAl and NiAl hydrotalcite (HT precursors, various methods for nickel introduction into HT structure, calcination conditions and promoters are discussed. HT-derived materials containing nickel generally exhibit high activity in DRM; however, the problem of preventing catalyst deactivation by coking, especially below 700 °C, is still an open question. The proposed solutions in the literature include: catalyst regeneration either in oxygen atmosphere or via hydrogasification; or application of various promoters, such as Zr, Ce or La, which was proven to enhance catalytic stability.

Mechanism of carbon deposit - removal in methane dry reforming on supported metal catalysts

NARCIS (Netherlands)

Nagaoka, K.; Nagaoka, K.; Seshan, Kulathuiyer; Lercher, J.A.; Aika, A.; Iglesia, E.; Spivey, J.J.; Fleisc, T.H.

2001-01-01

The greater resistance to coke deposition for Pt/ZrO2 compared to Pt/Al2O3 in the CH4/CO2 reaction has been attributed to the higher reactivity of coke with CO2 on Pt/ZrO2 [1]. Hence, in this communication, the reaction of coke derived from methane (CHx: which is an intermediated in the reforming

Plasma catalytic reforming of methane

Energy Technology Data Exchange (ETDEWEB)

Bromberg, L.; Cohn, D.R.; Rabinovich, A. [Massachusetts Inst. of Technology, Cambridge, MA (United States). Plasma Science and Fusion Center; Alexeev, N. [Russian Academy of Sciences, Moscow (Russian Federation). Baikov Inst. of Metallurgy

1998-08-01

Thermal plasma technology can be efficiently used in the production of hydrogen and hydrogen-rich gases from methane and a variety of fuels. This paper describes progress in plasma reforming experiments and calculations of high temperature conversion of methane using heterogeneous processes. The thermal plasma is a highly energetic state of matter that is characterized by extremely high temperatures (several thousand degrees Celsius) and high degree of dissociation and substantial degree of ionization. The high temperatures accelerate the reactions involved in the reforming process. Hydrogen-rich gas (50% H{sub 2}, 17% CO and 33% N{sub 2}, for partial oxidation/water shifting) can be efficiently made in compact plasma reformers. Experiments have been carried out in a small device (2--3 kW) and without the use of efficient heat regeneration. For partial oxidation/water shifting, it was determined that the specific energy consumption in the plasma reforming processes is 16 MJ/kg H{sub 2} with high conversion efficiencies. Larger plasmatrons, better reactor thermal insulation, efficient heat regeneration and improved plasma catalysis could also play a major role in specific energy consumption reduction and increasing the methane conversion. A system has been demonstrated for hydrogen production with low CO content ({approximately} 1.5%) with power densities of {approximately} 30 kW (H{sub 2} HHV)/liter of reactor, or {approximately} 10 m{sup 3}/hr H{sub 2} per liter of reactor. Power density should further increase with increased power and improved design.

METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

Directory of Open Access Journals (Sweden)

Rafael García

2015-05-01

Full Text Available The influence of metal loading and support surface functional groups (SFG on methane dry reforming (MDR over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

Parametric study on catalytic tri-reforming of methane for syngas production

International Nuclear Information System (INIS)

Chein, Rei-Yu; Wang, Chien-Yu; Yu, Ching-Tsung

2017-01-01

A two-dimensional numerical model for syngas production from tri-reforming of methane (TRM) in adiabatic tubular fixed-bed reactors was established. From the results obtained, it was found that reactant must be preheated to certain temperatures for TRM activation. Although the delay factor accounting for the varying catalytic bed activities produced different temperature and species mole fraction profiles in the reactor upstream, the reactor performance was delay factor independent if the reactor outlet results were used because nearly identical temperature and species mole fraction variations were obtained at the reactor downstream. The numerical results also indicated that reverse water-gas shift reaction plays an important role for H 2 and CO yields. With higher O 2 in reactant, high temperature resulted, leading to lower H 2 /CO ratio. The absence of H 2 O in the reactant caused dry reforming of methane as the dominant reaction, resulting in H 2 /CO ratio close to unity. With the absence of CO 2 in the reactant, steam reforming of methane was the dominant reaction, resulting in H 2 /CO ratio close to 3. Using flue gas from combustion as TRM feedstock, it was found that H 2 /CO ratio was enhanced using lower CH 4 amount in reactant. High-temperature flue gas was suggested for TRM for the activation requirement. - Highlights: • Reactant must be preheated to certain temperature for tri-reforming of methane (TRM) activation. • A delay factor is used to account for varying catalytic activity. • TRM performance is delay factor independent when reactor outlet results are used. • Water-gas shift reaction plays an important role in H 2 yield, CO yield and H 2 /CO ratio in TRM. • Low CH 4 and high temperature are suggested when flue gas is used in TRM.

Thermochemical performance analysis of solar driven CO_2 methane reforming

International Nuclear Information System (INIS)

Fuqiang, Wang; Jianyu, Tan; Huijian, Jin; Yu, Leng

2015-01-01

Increasing CO_2 emission problems create urgent challenges for alleviating global warming, and the capture of CO_2 has become an essential field of scientific research. In this study, a finite volume method (FVM) coupled with thermochemical kinetics was developed to analyze the solar driven CO_2 methane reforming process in a metallic foam reactor. The local thermal non-equilibrium (LTNE) model coupled with radiative heat transfer was developed to provide more temperature information. A joint inversion method based on chemical process software and the FVM coupled with thermochemical kinetics was developed to obtain the thermochemical reaction parameters and guarantee the calculation accuracy. The detailed thermal and thermochemical performance in the metal foam reactor was analyzed. In addition, the effects of heat flux distribution and porosity on the solar driven CO_2 methane reforming process were analyzed. The numerical results can serve as theoretical guidance for the solar driven CO_2 methane reforming application. - Highlights: • Solar driven CO_2 methane reforming process in metal foam reactor is analyzed. • FVM with chemical reactions was developed to analyze solar CO_2 methane reforming. • A joint inversion method was developed to obtain thermochemical reaction parameters. • Results can be a guidance for the solar driven CO_2 methane reforming application.

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)

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)

DFT study on dry reforming of methane over Ni2Fe overlayer of Ni(1 1 1) surface

Science.gov (United States)

Xu, Li-li; Wen, Hong; Jin, Xin; Bing, Qi-ming; Liu, Jing-yao

2018-06-01

We reported the complete catalytic cycle of dry reforming of methane (DRM) on Ni2Fe overlayer of Ni(1 1 1) surface by periodic density functional theory (DFT) calculations. The pathways for dehydrogenation of CH4 and CO2 activation were located. Our results demonstrate that compared with pure Ni(1 1 1) surface, the introduction Fe into Ni increases the energy barrier of CH dissociation to carbon and hydrogen atoms, thereby suppressing coke deposition on the surface, while it promotes the H-induced CO2 activation pathway to form OH radical, and thus not only the surface oxygen but also OH are responsible for the oxidation of CHx (x = 0,1) on the Ni2Fe overlayer. The most favorable pathway of CH/C oxidation is found to be CH∗ + OH∗ → CHOH∗ → CHO∗ + H∗ → CO∗ + 2H∗, with the rate-limiting energy barrier of 1.12 eV. Furthermore, since Fe is oxidized partially to FeO leading to a partial dealloying under DRM conditions, we also studied the surface-carbon removal and the activity for the reforming of methane on the FeO ribbon supported Ni(1 1 1) (FeO/Ni) interface by DFT+U method. The surface C reacts with lattice oxygen of FeO to produce CO via a Mars-van Krevelen (MvK) mechanism, with a very lower energy barrier of 0.16 eV. The present results show that the introduction of Fe into Ni has a positive effect on the activity toward DRM and has an improved coke resistance.

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)

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

KAUST Repository

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; Anjum, Dalaver; Kanoun, Mohammed; Scaranto, Jessica; Hedhili, Mohamed Nejib; Khalid, Syed; Laveille, Paco; D'Souza, Lawrence; Clo, Alain M.; Basset, Jean-Marie

2015-01-01

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.

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.

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)

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.

Effect of NiAl2O4 Formation on Ni/Al2O3 Stability during Dry Reforming of Methane

KAUST Repository

Zhou, Lu; Li, Lidong; Wei, Nini; Li, Jun; Basset, Jean-Marie

2015-01-01

A series of alumina-supported Ni catalysts were prepared to examine their activity and carbon deposition during dry reforming of methane (DRM). With an increase in the final calcination temperature to T=900 °C to form exclusively NiAl2O4, a catalyst with strong metal–support interactions was obtained. During a long-term DRM reaction (of about t=100 h) at T=700 °C and with CH4/CO2=1:1, reduced Ni (from NiAl2O4) showed a high resistance to sintering and coking. The DRM kinetics behaviors of the catalysts calcined at different temperatures were also investigated. Carbon growth models were proposed to rationalize the different carbon morphologies observed on the catalysts.

Effect of NiAl2O4 Formation on Ni/Al2O3 Stability during Dry Reforming of Methane

KAUST Repository

Zhou, Lu

2015-07-16

A series of alumina-supported Ni catalysts were prepared to examine their activity and carbon deposition during dry reforming of methane (DRM). With an increase in the final calcination temperature to T=900 °C to form exclusively NiAl2O4, a catalyst with strong metal–support interactions was obtained. During a long-term DRM reaction (of about t=100 h) at T=700 °C and with CH4/CO2=1:1, reduced Ni (from NiAl2O4) showed a high resistance to sintering and coking. The DRM kinetics behaviors of the catalysts calcined at different temperatures were also investigated. Carbon growth models were proposed to rationalize the different carbon morphologies observed on the catalysts.

In situ NAP-XPS spectroscopy during methane dry reforming on ZrO2/Pt(1 1 1) inverse model catalyst

Science.gov (United States)

Rameshan, C.; Li, H.; Anic, K.; Roiaz, M.; Pramhaas, V.; Rameshan, R.; Blume, R.; Hävecker, M.; Knudsen, J.; Knop-Gericke, A.; Rupprechter, G.

2018-07-01

Due to the need of sustainable energy sources, methane dry reforming is a useful reaction for conversion of the greenhouse gases CH4 and CO2 to synthesis gas (CO  +  H2). Syngas is the basis for a wide range of commodity chemicals and can be utilized for fuel production via Fischer–Tropsch synthesis. The current study focuses on spectroscopic investigations of the surface and reaction properties of a ZrO2/Pt inverse model catalyst, i.e. ZrO2 particles (islands) grown on a Pt(1 1 1) single crystal, with emphasis on in situ near ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) during MDR reaction. In comparison to technological systems, model catalysts facilitate characterization of the surface (oxidation) state, surface adsorbates, and the role of the metal-support interface. Using XPS and infrared reflection absorption spectroscopy we demonstrated that under reducing conditions (UHV or CH4) the ZrO2 particles transformed to an ultrathin ZrO2 film that started to cover (wet) the Pt surface in an SMSI-like fashion, paralleled by a decrease in surface/interface oxygen. In contrast, (more oxidizing) dry reforming conditions with a 1:1 ratio of CH4 and CO2 were stabilizing the ZrO2 particles on the model catalyst surface (or were even reversing the strong metal support interaction (SMSI) effect), as revealed by in situ XPS. Carbon deposits resulting from CH4 dissociation were easily removed by CO2 or by switching to dry reforming conditions (673–873 K). Thus, at these temperatures the active Pt surface remained free of carbon deposits, also preserving the ZrO2/Pt interface.

An afterburner-powered methane/steam reformer for a solid oxide fuel cells application

Science.gov (United States)

Mozdzierz, Marcin; Chalusiak, Maciej; Kimijima, Shinji; Szmyd, Janusz S.; Brus, Grzegorz

2018-04-01

Solid oxide fuel cell (SOFC) systems can be fueled by natural gas when the reforming reaction is conducted in a stack. Due to its maturity and safety, indirect internal reforming is usually used. A strong endothermic methane/steam reforming process needs a large amount of heat, and it is convenient to provide thermal energy by burning the remainders of fuel from a cell. In this work, the mathematical model of afterburner-powered methane/steam reformer is proposed. To analyze the effect of a fuel composition on SOFC performance, the zero-dimensional model of a fuel cell connected with a reformer is formulated. It is shown that the highest efficiency of a solid oxide fuel cell is achieved when the steam-to-methane ratio at the reforming reactor inlet is high.

Thermal Modeling and Management of Solid Oxide Fuel Cells Operating with Internally Reformed Methane

Science.gov (United States)

Wu, Yiyang; Shi, Yixiang; Cai, Ningsheng; Ni, Meng

2018-06-01

A detailed three-dimensional mechanistic model of a large-scale solid oxide fuel cell (SOFC) unit running on partially pre-reformed methane is developed. The model considers the coupling effects of chemical and electrochemical reactions, mass transport, momentum and heat transfer in the SOFC unit. After model validation, parametric simulations are conducted to investigate how the methane pre-reforming ratio affects the transport and electrochemistry of the SOFC unit. It is found that the methane steam reforming reaction has a "smoothing effect", which can achieve more uniform distributions of gas compositions, current density and temperature among the cell plane. In the case of 1500 W/m2 power density output, adding 20% methane absorbs 50% of internal heat production inside the cell, reduces the maximum temperature difference inside the cell from 70 K to 22 K and reduces the cathode air supply by 75%, compared to the condition of completely pre-reforming of methane. Under specific operating conditions, the pre-reforming ratio of methane has an optimal range for obtaining a good temperature distribution and good cell performance.

Production of hydrogen via methane reforming using atmospheric pressure microwave plasma

Energy Technology Data Exchange (ETDEWEB)

Jasinski, Mariusz; Dors, Miroslaw [Centre for Plasma and Laser Engineering, The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences, Fiszera 14, 80-952 Gdansk (Poland); Mizeraczyk, Jerzy [Centre for Plasma and Laser Engineering, The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences, Fiszera 14, 80-952 Gdansk (Poland); Department of Marine Electronics, Gdynia Maritime University, Morska 83, 81-225 Gdynia (Poland)

2008-06-15

In this paper, results of hydrogen production via methane reforming in the atmospheric pressure microwave plasma are presented. A waveguide-based nozzleless cylinder-type microwave plasma source (MPS) was used to convert methane into hydrogen. Important advantages of the presented waveguide-based nozzleless cylinder-type MPS are: stable operation in various gases (including air) at high flow rates, no need for a cooling system, and impedance matching. The plasma generation was stabilized by an additional swirled nitrogen flow (50 or 100 l min{sup -1}). The methane flow rate was up to 175 l min{sup -1}. The absorbed microwave power could be changed from 3000 to 5000 W. The hydrogen production rate and the corresponding energy efficiency in the presented methane reforming by the waveguide-based nozzleless cylinder-type MPS were up to 255 g[H{sub 2}] h{sup -1} and 85 g[H{sub 2}] kWh{sup -1}, respectively. These parameters are better than those typical of the conventional methods of hydrogen production (steam reforming of methane and water electrolysis). (author)

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

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.

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.

Kinetic Study of Nonequilibrium Plasma-Assisted Methane Steam Reforming

Directory of Open Access Journals (Sweden)

Hongtao Zheng

2014-01-01

Full Text Available To develop a detailed reaction mechanism for plasma-assisted methane steam reforming, a comprehensive numerical and experimental study of effect laws on methane conversion and products yield is performed at different steam to methane molar ratio (S/C, residence time s, and reaction temperatures. A CHEMKIN-PRO software with sensitivity analysis module and path flux analysis module was used for simulations. A set of comparisons show that the developed reaction mechanism can accurately predict methane conversion and the trend of products yield in different operating conditions. Using the developed reaction mechanism in plasma-assisted kinetic model, the reaction path flux analysis was carried out. The result shows that CH3 recombination is the limiting reaction for CO production and O is the critical species for CO production. Adding 40 wt.% Ni/SiO2 in discharge region has significantly promoted the yield of H2, CO, or CO2 in dielectric packed bed (DPB reactor. Plasma catalytic hybrid reforming experiment verifies the reaction path flux analysis tentatively.

Liquid hydrogen production via hydrogen sulfide methane reformation

Science.gov (United States)

Huang, Cunping; T-Raissi, Ali

Hydrogen sulfide (H 2S) methane (CH 4) reformation (H 2SMR) (2H 2S + CH 4 = CS 2 + 4H 2) is a potentially viable process for the removal of H 2S from sour natural gas resources or other methane containing gases. Unlike steam methane reformation that generates carbon dioxide as a by-product, H 2SMR produces carbon disulfide (CS 2), a liquid under ambient temperature and pressure-a commodity chemical that is also a feedstock for the synthesis of sulfuric acid. Pinch point analyses for H 2SMR were conducted to determine the reaction conditions necessary for no carbon lay down to occur. Calculations showed that to prevent solid carbon formation, low inlet CH 4 to H 2S ratios are needed. In this paper, we analyze H 2SMR with either a cryogenic process or a membrane separation operation for production of either liquid or gaseous hydrogen. Of the three H 2SMR hydrogen production flowsheets analyzed, direct liquid hydrogen generation has higher first and second law efficiencies of exceeding 80% and 50%, respectively.

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)

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.

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].

Liquid hydrogen production via hydrogen sulfide methane reformation

Energy Technology Data Exchange (ETDEWEB)

Huang, Cunping; T-Raissi, Ali [University of Central Florida, Florida Solar Energy Center, 1769 Clearlake Road, Cocoa, FL 32922 (United States)

2008-01-03

Hydrogen sulfide (H{sub 2}S) methane (CH{sub 4}) reformation (H{sub 2}SMR) (2H{sub 2}S + CH{sub 4} = CS{sub 2} + 4H{sub 2}) is a potentially viable process for the removal of H{sub 2}S from sour natural gas resources or other methane containing gases. Unlike steam methane reformation that generates carbon dioxide as a by-product, H{sub 2}SMR produces carbon disulfide (CS{sub 2}), a liquid under ambient temperature and pressure - a commodity chemical that is also a feedstock for the synthesis of sulfuric acid. Pinch point analyses for H{sub 2}SMR were conducted to determine the reaction conditions necessary for no carbon lay down to occur. Calculations showed that to prevent solid carbon formation, low inlet CH{sub 4} to H{sub 2}S ratios are needed. In this paper, we analyze H{sub 2}SMR with either a cryogenic process or a membrane separation operation for production of either liquid or gaseous hydrogen. Of the three H{sub 2}SMR hydrogen production flowsheets analyzed, direct liquid hydrogen generation has higher first and second law efficiencies of exceeding 80% and 50%, respectively. (author)

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.

Development of methane conversion improvement method by recycling of residual methane for steam reforming as a part of R and D of HTGR-hydrogen production system

International Nuclear Information System (INIS)

Inagaki, Yoshiyuki; Haga, Katsuhiro; Aita, Hideki; Sekita, Kenji; Hino, Ryutaro; Koiso, Hiroshi.

1998-01-01

The purpose of the present study is to improve methane conversion for an HTGR-steam reforming system by recycling of residual methane. The residual methane in a product gas after steam reforming was recycled with a gas separator of polyimide membrane. Gas separation characteristics of the separator were investigated experimentally and numerically, and an experimental study on recycling system was carried out. The results showed that the recycling system improves apparent methane conversion, ratio of methane conversion to methane supply from a cylinder, from 20 to 32% compared with those without recycling. (author)

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.

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.

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.

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.

Hydrogen production by methane reforming based on micro-gap discharge

International Nuclear Information System (INIS)

Liu, N N; Wang, M X; Liu, K Y; Bai, M D

2013-01-01

Based on micro-gap strong ionization discharge, this paper presents a study of hydrogen production by methane reforming at room temperature and atmospheric pressure without catalyst. Influence rules of conversion of methane and production of hydrogen were studied by changing discharge power and feed gas flow rate. Results show that when the discharge power was about 341 W, the discharge gap was 0.47 mm and the flow rate of feed gas was 100 mL min −1 , the conversion of methane and yield of hydrogen reached optimization. The conversion rate of methane and the highest yield of hydrogen were 68.14 % and 51.34 %, respectively.

High temperature energy storage performances of methane reforming with carbon dioxide in a tubular packed reactor

International Nuclear Information System (INIS)

Lu, Jianfeng; Chen, Yuan; Ding, Jing; Wang, Weilong

2016-01-01

Highlights: • Energy storage of methane reforming in a tubular packed reactor is investigated. • Thermochemical storage efficiency approaches maximum at optimal temperature. • Sensible heat and heat loss play important roles in the energy storage system. • The reaction and energy storage models of methane reforming reactor are established. • The simulated methane conversion and energy storage efficiency fit with experiments. - Abstract: High temperature heat transfer and energy storage performances of methane reforming with carbon dioxide in tubular packed reactor are investigated under different operating conditions. Experimental results show that the methane reforming in tubular packed reactor can efficiently store high temperature thermal energy, and the sensible heat and heat loss besides thermochemical energy storage play important role in the total energy storage process. When the operating temperature is increased, the thermochemical storage efficiency first increases for methane conversion rising and then decreases for heat loss rising. As the operating temperate is 800 °C, the methane conversion is 79.6%, and the thermochemical storage efficiency and total energy efficiency can be higher than 47% and 70%. According to the experimental system, the flow and reaction model of methane reforming is established using the laminar finite-rate model and Arrhenius expression, and the simulated methane conversion and energy storage efficiency fit with experimental data. Along the flow direction, the fluid temperature in the catalyst bed first decreases because of the endothermic reaction and then increases for the heat transfer from reactor wall. As a conclusion, the maximum thermochemical storage efficiency will be obtained under optimal operating temperature and optimal flow rate, and the total energy efficiency can be increased by the increase of bed conductivity and decrease of heat loss coefficient.

Recent Advances in Supported Metal Catalysts for Syngas Production from Methane

OpenAIRE

Mohanned Mohamedali; Amr Henni; Hussameldin Ibrahim

2018-01-01

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...

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.

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.

Numerical analysis of performance of steam reformer of methane reforming hydrogen production system connected with high-temperature gas-cooled reactor

International Nuclear Information System (INIS)

Yin Huaqiang; Jiang Shengyao; Zhang Youjie

2007-01-01

Methane conversion rate and hydrogen output are important performance indexes of the steam reformer. The paper presents numerical analysis of performance of the reformer connected with high-temperature gas-cooled reactor HTR-10. Setting helium inlet flow rate fixed, performance of the reformer was examined with different helium inlet temperature, pressure, different process gas temperature, pressure, flow rate, and different steam to carbon ratio. As the range concerned, helium inlet temperature has remarkable influence on the performance, and helium inlet temperature, process gas temperature and pressure have little influence on the performance, and improving process gas flow rate, methane conversion rate decreases and hydrogen output increases, however improving steam to carbon ratio has reverse influence on the performance. (authors)

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

Analysis on Operating Parameter Design to Steam Methane Reforming in Heat Application RDE

Science.gov (United States)

Dibyo, Sukmanto; Sunaryo, Geni Rina; Bakhri, Syaiful; Zuhair; Irianto, Ign. Djoko

2018-02-01

The high temperature reactor has been developed with various power capacities and can produce electricity and heat application. One of heat application is used for hydrogen production. Most hydrogen production occurs by steam reforming that operated at high temperature. This study aims to analyze the feasibility of heat application design of RDE reactor in the steam methane reforming for hydrogen production using the ChemCAD software. The outlet temperature of cogeneration heat exchanger is analyzed to be applied as a feed of steam reformer. Furthermore, the additional heater and calculating amount of fuel usage are described. Results show that at a low mass flow rate of feed, its can produce a temperature up to 480°C. To achieve the temperature of steam methane reforming of 850°C the additional fired heater was required. By the fired heater, an amount of fuel usage is required depending on the Reformer feed temperature produced from the heat exchanger of the cogeneration system.

Dry (CO_2) 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 to

Synthesis of carbon-supported nickel catalysts for the dry reforming of CH{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Fidalgo, B.; Zubizarreta, L.; Bermudez, J.M.; Arenillas, A.; Menendez, J.A. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain)

2010-07-15

A series of carbon-based nickel (Ni) catalysts was prepared in order to investigate the effect of the preparation method on the dispersion of Ni and its final catalytic activity in the dry reforming of methane, i.e. CH{sub 4} + CO{sub 2} 2H{sub 2} + 2CO. Three parameters were studied: (i) the influence of the surface chemistry of the carbon used as support; (ii) the method of drying (conventional vs. microwave drying); and, (iii) the temperature of the reduction stage. In order to study the role of the surface chemistry of the commercial activated carbon used as support, the active carbon was tested as received and oxidized. Although a better Ni dispersion was achieved over the oxidized support, the conversions were much lower. It was also found that microwave drying offers various advantages over conventional drying, the main one being that less time is required to prepare the catalyst. Two reduction temperatures were used (300 and 500 C), being found that it is necessary to adjust this parameter to prevent the Ni particles from sintering. (author)

In silico search for novel methane steam reforming catalysts

DEFF Research Database (Denmark)

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

2013-01-01

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...

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

Indian Academy of Sciences (India)

T V Sagar

C, the sol–gel catalysts reached their maximum activity in terms of both CH4 and ... the attention of researchers recently.5,6 Reforming of methane with carbon ..... bands can be divided into four zones, with 2–3 peaks in each zone. In the first ...

Biogas reforming over multi walled carbon nanotubes with Co-Mo/MgO nanoparticles

Science.gov (United States)

Khavarian, Mehrnoush; Mohamed, Abdul Rahman

2017-12-01

The utilization of biogas for the production of valuable chemicals is among the very important processes in the energy research field. The most suitable process for biogas reforming is dry reforming of methane. An obvious drawback is the variable composition of biogas rather than the stoichiometrically equimolar quantities of methane and carbon dioxide. Moreover, activating the methane and carbon dioxide molecules in the reforming reaction provides many challenges in exploring new concepts and opportunities for development of unique catalysts. In the present work, the catalytic activity behavior of Co-Mo-MgO/multi-walled carbon nanotubes (MWCNTs) nanocomposite in dry reforming was investigated with different CO2/CH4 feed ratio to evaluate the performance of this catalyst for biogas reforming reaction. It was found that conversions of methane and carbon dioxide were greatly influenced by the feed gas ratio. The CH4 and CO2 conversions are 83 % and 87 % at the reaction temperature of 825 °C, GHSV of 175 L/h.gcat and CO2/CH4 feed ratio of unity. The minimum carbon deposition rate is observed at the CO2/CH4 feed ratio of 0.6 which is 0.080 gc/gcat-h.

Reaction phenomena of catalytic partial oxidation of methane under the impact of carbon dioxide addition and heat recirculation

International Nuclear Information System (INIS)

Chen, Wei-Hsin; Lin, Shih-Cheng

2015-01-01

The reaction phenomena of CPOM (catalytic partial oxidation of methane) in a Swiss-roll reactor are studied numerically where a rhodium-based catalyst bed is embedded at the center of the reactor. CO 2 is added into the feed gas and excess enthalpy recovery is performed to evaluate their influences on CPOM performance. In the study, the mole ratio of O 2 to CH 4 (O 2 /CH 4 ratio) is fixed at 0.5 and the mole ratio of CO 2 to O 2 (CO 2 /O 2 ratio) is in the range of 0–2. The results reveal that CO 2 addition into the influent has a slight effect on methane combustion, but significantly enhances dry reforming and suppresses steam reforming. The reaction extents of steam reforming and dry reforming in CPOM without heat recovery and CO 2 addition are in a comparable state. Once CO 2 is added into the feed gas, the dry reforming is enhanced, thereby dominating CH 4 consumption. Compared to the reactor without excess enthalpy recovery, heat recirculation drastically increases the maximum reaction temperature and CH 4 conversion in the catalyst bed; it also intensifies the H 2 selectivity, H 2 yield, CO 2 conversion, and syngas production rate. The predictions indicate that the heat recirculation is able to improve the syngas formation up to 45%. - Highlights: • Catalytic partial oxidation of methane with CO 2 addition and heat recovery is studied. • CO 2 addition has a slight effect on methane combustion. • CO 2 addition significantly enhances dry reforming and suppresses steam reforming. • Dry reforming dominates CH 4 consumption when CO 2 addition is large. • Heat recirculation can improve the syngas formation up to 45%

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.

Evaluation of an integrated methane autothermal reforming and high-temperature proton exchange membrane fuel cell system

International Nuclear Information System (INIS)

Authayanun, Suthida; Saebea, Dang; Patcharavorachot, Yaneeporn; Arpornwichanop, Amornchai

2015-01-01

The aim of this study was to investigate the performance and efficiency of an integrated autothermal reforming and HT-PEMFC (high-temperature proton exchange membrane fuel cell) system fueled by methane. Effect of the inclusion of a CO (carbon monoxide) removal process on the integrated HT-PEMFC system was considered. An increase in the S/C (steam-to-carbon) ratio and the reformer temperature can enhance the hydrogen fraction while the CO formation reduces with increasing S/C ratio. The fuel processor efficiency of the methane autothermal reformer with a WGS (water gas shift reactor) reactor, as the CO removal process, is higher than that without a WGS reactor. A higher fuel processor efficiency can be obtained when the feed of the autothermal reformer is preheated to the reformer temperature. Regarding the cell performance, the reformate gas from the methane reformer operated at T in  = T R and with a high S/C ratio is suitable for the HT-PEMFC system without a WGS reactor. When considering the HT-PEMFC system with a WGS reactor, the CO poisoning has less significant impact on the cell performance and the system can be operated over a broader range to minimize the required total active area. A WGS reactor is necessary for the methane autothermal reforming and HT-PEMFC integrated system with regard to the system efficiency. - Highlights: • An integrated autothermal reforming and HT-PEMFC system was studied. • The HT-PEMFC system with and without a CO removal process was considered. • Parametric analysis was performed to obtain a high system efficiency. • The HT-PEMFC system with the WGS reactor can be run over a broader range. • The efficiencies of the HT-PEMFC systems without and with a WGS reactor were reported

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.)

2D heat and mass transfer modeling of methane steam reforming for hydrogen production in a compact reformer

International Nuclear Information System (INIS)

Ni Meng

2013-01-01

Highlights: ► A heat and mass transfer model is developed for a compact reformer. ► Hydrogen production from methane steam reforming is simulated. ► Increasing temperature greatly increases the reaction rates at the inlet. ► Temperature in the downstream is increased at higher rate of heat supply. ► Larger permeability enhances gas flow and reaction rates in the catalyst layer. - Abstract: Compact reformers (CRs) are promising devices for efficient fuel processing. In CRs, a thin solid plate is sandwiched between two catalyst layers to enable efficient heat transfer from combustion duct to the reforming duct for fuel processing. In this study, a 2D heat and mass transfer model is developed to investigate the fundamental transport phenomenon and chemical reaction kinetics in a CR for hydrogen production by methane steam reforming (MSR). Both MSR reaction and water gas shift reaction (WGSR) are considered in the numerical model. Parametric simulations are performed to examine the effects of various structural/operating parameters, such as pore size, permeability, gas velocity, temperature, and rate of heat supply on the reformer performance. It is found that the reaction rates of MSR and WGSR are the highest at the inlet but decrease significantly along the reformer. Increasing the operating temperature raises the reaction rates at the inlet but shows very small influence in the downstream. For comparison, increasing the rate of heat supply raises the reaction rates in the downstream due to increased temperature. A high gas velocity and permeability facilitates gas transport in the porous structure thus enhances reaction rates in the downstream of the reformer.

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

Bi-reforming of methane from any source with steam and carbon dioxide exclusively to metgas (CO-2H2) for methanol and hydrocarbon synthesis.

Science.gov (United States)

Olah, George A; Goeppert, Alain; Czaun, Miklos; Prakash, G K Surya

2013-01-16

A catalyst based on nickel oxide on magnesium oxide (NiO/MgO) thermally activated under hydrogen is effective for the bi-reforming with steam and CO(2) (combined steam and dry reforming) of methane as well as natural gas in a tubular flow reactor at elevated pressures (5-30 atm) and temperatures (800-950 °C). By adjusting the CO(2)-to-steam ratio in the gas feed, the H(2)/CO ratio in the produced syn-gas could be easily adjusted in a single step to the desired value of 2 for methanol and hydrocarbon synthesis.

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.

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

Indian Academy of Sciences (India)

SOURABH MISHRA

2017-09-27

Sep 27, 2017 ... (Syn-gas, CO+H2) formation via steam reforming, dry reforming or partial oxidation of methane ... Micromeritics ASAP 2010 apparatus at liquid nitrogen tem- perature. Nitrogen (N2) was the adsorbate ... some runs were carried out in triplicate and mass balance for all the runs was measured. Runs with a ...

Preliminary assessment of synthesis gas production via hybrid steam reforming of methane and glycerol

NARCIS (Netherlands)

Balegedde Ramachandran, P.; van Rossum, G.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

2012-01-01

In this article, hybrid steam reforming (HSR) of desulphurized methane, together with crude glycerol, in existing commercial steam reformers to produce synthesis gas is proposed. The proposed concept consists of a gasifier to produce vapors, gases, and char from crude glycerol, which is coupled with

Internal reforming of methane in solid oxide fuel cell systems

Science.gov (United States)

Peters, R.; Dahl, R.; Klüttgen, U.; Palm, C.; Stolten, D.

Internal reforming is an attractive option offering a significant cost reduction, higher efficiencies and faster load response of a solid oxide fuel cell (SOFC) power plant. However, complete internal reforming may lead to several problems which can be avoided with partial pre-reforming of natural gas. In order to achieve high total plant efficiency associated with low energy consumption and low investment costs, a process concept has been developed based on all the components of the SOFC system. In the case of anode gas recycling an internal steam circuit exists. This has the advantage that there is no need for an external steam generator and the steam concentration in the anode gas is reduced. However, anode gas recycling has to be proven by experiments in a pre-reformer and for internal reforming. The addition of carbon dioxide clearly shows a decrease in catalyst activity, while for temperatures higher than 1000 K hydrogen leads to an increase of the measured methane conversion rates.

Catalytic reforming of methane to syngas in an oxygen-permeative membrane reactor

Energy Technology Data Exchange (ETDEWEB)

Urano, Takeshi; Kubo, Keiko; Saito, Tomoyuki; Hitomi, Atsushi, E-mail: turano@jp.tdk.com [Materials and Process Development Center, TDK Corporation 570-2, Matsugashita, Minamihatori, Narita, Chiba 286-8588 (Japan)

2011-05-15

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.

Methane-steam reforming by molten salt - membrane reactor using concentrated solar thermal energy

International Nuclear Information System (INIS)

Watanuki, K.; Nakajima, H.; Hasegawa, N.; Kaneko, H.; Tamaura, Y.

2006-01-01

By utilization of concentrated solar thermal energy for steam reforming of natural gas, which is an endothermic reaction, the chemical energy of natural gas can be up-graded. The chemical system for steam reforming of natural gas with concentrated solar thermal energy was studied to produce hydrogen by using the thermal storage with molten salt and the membrane reactor. The original steam reforming module with hydrogen permeable palladium membrane was developed and fabricated. Steam reforming of methane proceeded with the original module with palladium membrane below the decomposition temperature of molten salt (around 870 K). (authors)

Effects of key factors on solar aided methane steam reforming in porous medium thermochemical reactor

International Nuclear Information System (INIS)

Wang, Fuqiang; Tan, Jianyu; Ma, Lanxin; Leng, Yu

2015-01-01

Highlights: • Effects of key factors on chemical reaction for solar methane reforming are studied. • MCRT and FVM method coupled with UDFs is used to establish numerical model. • Heat and mass transfer model coupled with thermochemical reaction is established. • LTNE model coupled with P1 approximation is used for porous matrix solar reactor. • A formula between H 2 production and conductivity of porous matrix is put forward. - Abstract: With the aid of solar energy, methane reforming process can save up to 20% of the total methane consumption. Monte Carlo Ray Tracing (MCRT) method and Finite Volume Method (FVM) combined method are developed to establish the heat and mass transfer model coupled with thermochemical reaction kinetics for porous medium solar thermochemical reactor. In order to provide more temperature information, local thermal non-equilibrium (LTNE) model coupled with P1 approximation is established to investigate the thermal performance of porous medium solar thermochemical reaction. Effects of radiative heat loss and thermal conductivity of porous matrix on temperature distribution and thermochemical reaction for solar driven steam methane reforming process are numerically studied. Besides, the relationship between hydrogen production and thermal conductivity of porous matrix are analyzed. The results illustrate that hydrogen production shows a 3 order polynomial relation with thermal conductivity of porous matrix

First principles calculations and experimental insight into methane steam reforming over transition metal catalysts

DEFF Research Database (Denmark)

Jones, Glenn; Jakobsen, Jon Geest; Shim, Signe Sarah

2008-01-01

This paper presents a detailed analysis of the steam reforming process front first-principles calculations, supported by insight from experimental investigations. In the present work we employ recently recognised scaling relationships for adsorption energies of simple molecules adsorbed at pure...... metal Surfaces to develop an overview of the steam reforming process catalyzed by a range of transition metal surfaces. By combining scaling relationships with thermodynamic and kinetic analysis, we show that it is possible to determine the reactivity trends of the pure metals for methane steam...... in situ TEM measurements under a hydrogen atmosphere. The overall agreement between theory and experiment (at 773 K, 1 bar pressure and 10% conversion) is found to be excellent with Ru and Rh being the most active pure transition metals for methane steam reforming, while Ni, Ir, Pt, and Pd...

A theoretical study on the structure dependence of the steam methane reforming reaction by rhodium

NARCIS (Netherlands)

Grootel, van P.W.

2012-01-01

Steam methane reforming is an important industrial reaction for the conversion of methane with steam to synthesis gas, a mixture of carbon monoxide and hydrogen. Hydrogen is used in many applications, e.g. for hydrogenation purposes. It is also used for the production of bulk chemicals such as

Modeling and parametric simulations of solid oxide fuel cells with methane carbon dioxide reforming

International Nuclear Information System (INIS)

Ni, Meng

2013-01-01

Highlights: ► A 2D model is developed for solid oxide fuel cells (SOFCs). ► CH 4 reforming by CO 2 (MCDR) is included. ► SOFC with MCDR shows comparable performance with methane steam reforming SOFC. ► Increasing CO electrochemical oxidation greatly enhances the SOFC performance. ► Effects of potential and temperature on SOFC performance are also discussed. - Abstract: A two-dimensional model is developed to simulate the performance of solid oxide fuel cells (SOFCs) fed with CO 2 and CH 4 mixture. The electrochemical oxidations of both CO and H 2 are included. Important chemical reactions are considered in the model, including methane carbon dioxide reforming (MCDR), reversible water gas shift reaction (WGSR), and methane steam reforming (MSR). It’s found that at a CH 4 /CO 2 molar ratio of 50/50, MCDR and reversible WGSR significantly influence the cell performance while MSR is negligibly small. The performance of SOFC fed with CO 2 /CH 4 mixture is comparable to SOFC running on CH 4 /H 2 O mixtures. The electric output of SOFC can be enhanced by operating the cell at a low operating potential or at a high temperature. In addition, the development of anode catalyst with high activity towards CO electrochemical oxidation is important for SOFC performance enhancement. The model can serve as a useful tool for optimization of the SOFC system running on CH 4 /CO 2 mixtures

Internal reforming characteristics of cermet supported solid oxide fuel cell using yttria stabilized zirconia fed with partially reformed methane

Science.gov (United States)

Momma, Akihiko; Takano, Kiyonami; Tanaka, Yohei; Negishi, Akira; Kato, Ken; Nozaki, Ken; Kato, Tohru; Ichigi, Takenori; Matsuda, Kazuyuki; Ryu, Takashi

In order to investigate the internal reforming characteristics in a cermet supported solid oxide fuel cell (SOFC) using YSZ as the electrolyte, the concentration profiles of the gaseous species along the gas flow direction in the anode were measured. Partially reformed methane using a pre-reformer kept at a constant temperature is supplied to the center of the cell which is operated with a seal-less structure at the gas outlet. The anode gas is sucked in via silica capillaries to the initially evacuated gas tanks. The process is simultaneously carried out using five sampling ports. The sampled gas is analyzed by a gas chromatograph. Most of the measurements are made at the cell temperature (T cell) of 750 °C and at various temperatures of the pre-reformer (T ref) with various fuel utilizations (U f) of the cell. The composition of the fuel at the inlet of the anode was confirmed to be almost the same as that theoretically calculated assuming equilibrium at the temperature of the pre-reformer. The effect of internal reforming in the anode is clearly observed as a steady decrease in the methane concentration along the flow axis. The effect of the water-gas shift reaction is also observed as a decrease in the CO 2 concentration and an increase of CO concentration around the gas inlet region, as the water-gas shift reaction inversely proceeds when T cell is higher than T ref. The diffusion of nitrogen from the seal-less outermost edge is observed, and the diffusion is confirmed to be more significant as U f decreases. The observations are compared with the results obtained by the SOFC supported by lanthanum gallate electrolyte. With respect to the internal reforming performance, the cell investigated here is found to be more effective when compared to the previously reported electrolyte supported cell.

Rational design of Mg-Al mixed oxide-supported bimetallic catalysts for dry reforming of methane

Energy Technology Data Exchange (ETDEWEB)

Tsyganok, Andrey I. [Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, D' Iorio Hall, 10 Marie Curie Street, Ottawa, Ont. (Canada); Inaba, Mieko [Natural Gas Technology Development Team, Teikoku Oil Co., 9-23-30 Kitakarasuyama, Setagaya-ku, Tokyo 157-0061 (Japan); Tsunoda, Tatsuo; Uchida, Kunio; Suzuki, Kunio; Hayakawa, Takashi [Institute for Materials and Chemical Process, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Takehira, Katsuomi [Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527 (Japan)

2005-09-18

A novel synthetic strategy for preparing bimetallic Ru-M (M=Cr, Fe, Co, Ni and Cu) catalysts, supported on Mg-Al mixed oxide, has been introduced. It was based on a 'memory effect', i.e. on the ability of Mg-Al mixed oxide to reconstruct a layered structure upon rehydration with an aqueous solution. By repeated calcinations-rehydration cycles, layered double hydroxide (LDH) precursors of catalysts containing two different metals were synthesized. Bimetallic catalysts were then generated (1) in situ from LDH under methane reforming reaction conditions and (2) from mixed metal oxides obtained by preliminary LDH calcination. Among all the LDH-derived catalysts, a Ru{sup 0.1%}-Ni{sup 5.0%}/MgAlO{sub x} sample revealed the highest activity and selectivity to syngas, a suitable durability and a low coking capacity. A promoting effect of ruthenium on catalytic function of supported nickel was demonstrated. Preliminary LDH calcination was shown to markedly affect the catalytic activity of the derived catalysts and especially their coking properties.

Energy Analysis in Combined Reforming of Propane

Directory of Open Access Journals (Sweden)

K. Moon

2013-01-01

Full Text Available Combined (steam and CO2 reforming is one of the methods to produce syngas for different applications. An energy requirement analysis of steam reforming to dry reforming with intermediate steps of steam reduction and equivalent CO2 addition to the feed fuel for syngas generation has been done to identify condition for optimum process operation. Thermodynamic equilibrium data for combined reforming was generated for temperature range of 400–1000°C at 1 bar pressure and combined oxidant (CO2 + H2O stream to propane (fuel ratio of 3, 6, and 9 by employing the Gibbs free energy minimization algorithm of HSC Chemistry software 5.1. Total energy requirement including preheating and reaction enthalpy calculations were done using the equilibrium product composition. Carbon and methane formation was significantly reduced in combined reforming than pure dry reforming, while the energy requirements were lower than pure steam reforming. Temperatures of minimum energy requirement were found in the data analysis of combined reforming which were optimum for the process.

Tri-reforming and combined reforming of methane for producing syngas with desired hydrogen/carbon monoxide ratios

Science.gov (United States)

Pan, Wei

This dissertation is an exploratory study of a new process concept for direct production of synthesis gas (CO + H2) with desired H 2/CO ratios (1.5--2.0) for methanol synthesis and F-T synthesis, using CO2 together with steam and unconverted O2 in flue gas from fossil fuel-fired electric power plants to react with methane or natural gas. This new process is called tri-reforming, referring to simultaneous CO2-steam-O2 reforming of methane or natural gas. This study included (1) The investigation of carbon formation in the tri-reforming process. For comparison, carbon formation in the combined reforming and CO2 reforming reaction was studied as well. (2) The effect of reaction conditions and feed compositions on equilibrium composition (e.g. H2/CO ratio) and equilibrium conversions in the tri-reforming process. (3) The role of catalysts in the tri-reforming process, especially the effect of catalysts on CO2 conversion in the presence of H 2O and O2. It was clearly evidenced from this study that CO in the product stream is probably the major source of carbon over Ni/Al2O3 in the equimolar CO2-CH4 reforming at 650°C and 1 atm. Addition of either O2 or H2O into the CO 2 reforming reaction system can suppress carbon formation. It was demonstrated that carbon-free operation can be achieved in the tri-reforming process. A thermodynamic comparison of tri-reforming with feed compositions of (H2O+CO2+0.5O2)/CH4 (mol ratio) = 1 showed that O2 improves equilibrium CH4 conversion, yet greatly decreases equilibrium CO2 conversion. H2O in tri-reforming has a significant effect on the H2/CO ratio in the products, while O2 has a minor effect. A kinetic study and catalytic performance tests indicated that the support in a supported catalyst has a significant role in enhancing CO2 conversion to CO in the presence of H2O and O2 in tri-reforming. The Ni/MgO catalyst showed superior performance with close to equilibrium CH4 and CO2 conversions at 850°C, 1 atm, and 32,000 ml

Comparison of packed bed and fluidized bed membrane reactors for methane reforming

NARCIS (Netherlands)

Gallucci, F.; van Sint Annaland, M.; Kuipers, J.A.M.

2009-01-01

In this work the performance of different membrane reactor concepts, both fluidized bed and packed bed membrane reactors, have been compared for the reforming of methane for the production of ultra-pure hydrogen. Using detailed theoretical models, the required membrane area to reach a given

Internal reforming characteristics of cermet supported solid oxide fuel cell using yttria stabilized zirconia fed with partially reformed methane

Energy Technology Data Exchange (ETDEWEB)

Momma, Akihiko; Takano, Kiyonami; Tanaka, Yohei; Negishi, Akira; Kato, Ken; Nozaki, Ken; Kato, Tohru [Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono Tsukuba Ibaraki, 305-8568 (Japan); Ichigi, Takenori; Matsuda, Kazuyuki; Ryu, Takashi [Application Development Project, Corporate R and D, NGK Insulators, Ltd., 2-56 Suda-cho Mizuho-ku Nagoya-shi Aichi, 467-8530 (Japan)

2009-08-01

In order to investigate the internal reforming characteristics in a cermet supported solid oxide fuel cell (SOFC) using YSZ as the electrolyte, the concentration profiles of the gaseous species along the gas flow direction in the anode were measured. Partially reformed methane using a pre-reformer kept at a constant temperature is supplied to the center of the cell which is operated with a seal-less structure at the gas outlet. The anode gas is sucked in via silica capillaries to the initially evacuated gas tanks. The process is simultaneously carried out using five sampling ports. The sampled gas is analyzed by a gas chromatograph. Most of the measurements are made at the cell temperature (T{sub cell}) of 750 C and at various temperatures of the pre-reformer (T{sub ref}) with various fuel utilizations (U{sub f}) of the cell. The composition of the fuel at the inlet of the anode was confirmed to be almost the same as that theoretically calculated assuming equilibrium at the temperature of the pre-reformer. The effect of internal reforming in the anode is clearly observed as a steady decrease in the methane concentration along the flow axis. The effect of the water-gas shift reaction is also observed as a decrease in the CO{sub 2} concentration and an increase of CO concentration around the gas inlet region, as the water-gas shift reaction inversely proceeds when T{sub cell} is higher than T{sub ref}. The diffusion of nitrogen from the seal-less outermost edge is observed, and the diffusion is confirmed to be more significant as U{sub f} decreases. The observations are compared with the results obtained by the SOFC supported by lanthanum gallate electrolyte. With respect to the internal reforming performance, the cell investigated here is found to be more effective when compared to the previously reported electrolyte supported cell. (author)

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

Science.gov (United States)

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

2014-01-01

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

Thermal and chemical analysis of carbon dioxide reforming of methane using the out-of-pile test facility

International Nuclear Information System (INIS)

Huang Ziyong; Ohashi, Hirofumi; Inagaki, Yoshiyuki

2000-03-01

In the Japan Atomic Energy Research Institute, a hydrogen production system is being designed to produce hydrogen by means of steam reforming of natural gas (its main composition is methane(CH 4 )) using nuclear heat (10 MW, 1178 K) supplied by the High Temperature Engineering Test Reactor (HTTR). Prior to coupling of the steam reforming system with the HTTR, an out-of-pile demonstration test was planned to confirm safety, controllability and performance of the steam reforming system under simulated operational conditions of the prototype. The out-of-pile test facility simulates key components downstream to an intermediate heat exchanger of the HTTR hydrogen production system on a scale of 1 : 30 and has a hydrogen production capacity of 110 Nm 3 /h using an electric heater as a reactor substitute. The test facility is presently under construction. Reforming of natural gas with carbon dioxide CO 2 (CO 2 reforming) using the out-of-pile test facility is also being considered. In recent years, catalytic reforming of natural gas with CO 2 to synthesis gas (CO and H 2 ) has been proposed as one of the most promising technologies for utilization of those two greenhouse gases. Numerical analysis on heat and mass balance has practical significance in CO 2 reforming when the steam reforming process is adopted in the out-of-pile test. Numerical analysis of CO 2 reforming and reforming of natural gas with CO 2 and steam (CO 2 +H 2 O reforming) have been carried out using the mathematical model. Results such as the methane conversion rate, product gas composition, and the components temperature distribution considering the effects of helium gas temperature, reforming pressure, molar ratio of process gases and so on have been obtained in the numerical analysis. Heat and mass balance of the out-of-pile test facility considering chemical reactions are evaluated well. The methane conversation rates are about 0.36 and 0.35 which correspond to the equilibrium at 1085 and 1100 K for

Thermal and chemical analysis of carbon dioxide reforming of methane using the out-of-pile test facility

Energy Technology Data Exchange (ETDEWEB)

Huang Ziyong [Institute of Nuclear Energy Technology, Tsinghua University (China); Ohashi, Hirofumi; Inagaki, Yoshiyuki [Department of Advanced Nuclear Heat Technology, Oarai Research Establishment, Japan Atomic Energy Research Institute, Oarai, Ibaraki (Japan)

2000-03-01

In the Japan Atomic Energy Research Institute, a hydrogen production system is being designed to produce hydrogen by means of steam reforming of natural gas (its main composition is methane(CH{sub 4})) using nuclear heat (10 MW, 1178 K) supplied by the High Temperature Engineering Test Reactor (HTTR). Prior to coupling of the steam reforming system with the HTTR, an out-of-pile demonstration test was planned to confirm safety, controllability and performance of the steam reforming system under simulated operational conditions of the prototype. The out-of-pile test facility simulates key components downstream to an intermediate heat exchanger of the HTTR hydrogen production system on a scale of 1 : 30 and has a hydrogen production capacity of 110 Nm{sup 3}/h using an electric heater as a reactor substitute. The test facility is presently under construction. Reforming of natural gas with carbon dioxide CO{sub 2} (CO{sub 2} reforming) using the out-of-pile test facility is also being considered. In recent years, catalytic reforming of natural gas with CO{sub 2} to synthesis gas (CO and H{sub 2}) has been proposed as one of the most promising technologies for utilization of those two greenhouse gases. Numerical analysis on heat and mass balance has practical significance in CO{sub 2} reforming when the steam reforming process is adopted in the out-of-pile test. Numerical analysis of CO{sub 2} reforming and reforming of natural gas with CO{sub 2} and steam (CO{sub 2}+H{sub 2}O reforming) have been carried out using the mathematical model. Results such as the methane conversion rate, product gas composition, and the components temperature distribution considering the effects of helium gas temperature, reforming pressure, molar ratio of process gases and so on have been obtained in the numerical analysis. Heat and mass balance of the out-of-pile test facility considering chemical reactions are evaluated well. The methane conversation rates are about 0.36 and 0.35 which

Theoretical comparison of packed bed and fluidized bed membrane reactors for methane reforming

NARCIS (Netherlands)

Gallucci, F.; van Sint Annaland, M.; Kuipers, J.A.M.

2010-01-01

In this theoretical work the performance of different membrane reactor concepts, both fluidized bed and packed bed membrane reactors, has been compared for ultra-pure hydrogen production via methane reforming. Using detailed theoretical models, the required membrane area to reach a given conversion

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 ... Synthesis gas; H2 production; dry-reforming of biogas; MgO-NiO catalyst. 1. Introduction ... digestion in the palm-oil industry to reach the water- quality standards for .... Surfer Analyzer) nitrogen adsorption-desorption analyzer.

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....

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

Directory of Open Access Journals (Sweden)

Yunfei Yan

2014-01-01

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

A PVTC system integrating photon-enhanced thermionic emission and methane reforming for efficient solar power generation

Institute of Scientific and Technical Information of China (English)

Wenjia Li; Hongsheng Wang; Yong Hao

2017-01-01

A new photovoltaic-thermochemical (PVTC) conceptual system integrating photon-enhanced thermionic emission (PETE) and methane steam reforming is proposed.Major novelty of the system lies in its potential adaptivity to primary fuels (e.g.methane) and high efficiencies of photovoltaic and thermochemical power generation,both of which result from its operation at much elevated temperatures (700-1000 ℃)compared with conventional photovoltaic-thermal (PVT) systems.Analysis shows that an overall power generation efficiency of 45.3％ and a net solar-to-electric efficiency of 39.1％ could be reached at an operating temperature of 750 ℃,after considering major losses during solar energy capture and conversion processes.The system is also featured by high solar share (37％) in the total power output,as well as high energy storage capability and very low CO2 emissions,both enabled by the integration of methane reforming with photovoltaic generation at high temperatures.

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.)

Dry reforming of methane via plasma-catalysis: influence of the catalyst nature supported on alumina in a packed-bed DBD configuration

Science.gov (United States)

Brune, L.; Ozkan, A.; Genty, E.; Visart de Bocarmé, T.; Reniers, F.

2018-06-01

These days, the consideration of CO2 as a feedstock has become the subject of more interest. The reutilization of CO2 is already possible via cold plasma techniques operating at atmospheric pressure. A promising technology is the dielectric barrier discharge (DBD). In most cases DBDs exhibit a low energy efficiency for CO2 conversion. However, several routes can be used to increase this efficiency and hence, the product formation. One of these routes is the packed-bed DBD configuration with porous beads inside the gap of the DBD, which also allows the coupling of plasma with catalysis. Catalysts can be introduced in such a configuration to exploit the synergistic effect between plasma and catalytically active surfaces, leading to a more efficient process. In this article, the dry reforming of methane (DRM) is studied, which aims to convert both CO2 and CH4, another greenhouse gas, at the same time. The conversions and energy costs of the DRM process are investigated and compared in both the packed-bed DBD configurations containing catalysts (Co, Cu or Ni) and the classical DBD. The change in filamentary behavior is studied in detail and correlated with the obtained conversions using gas chromatography, mass spectrometry and using an oscilloscope. A characterization of the catalysts on the beads is also carried out. Both the CO2 and CH4 conversions are clearly increased with the plasma-catalysis. Moreover, CH4 conversions as high as 90% can be obtained in certain conditions with copper catalysts.

Projected hydrogen cost from methane reforming for North America 2015-2050

International Nuclear Information System (INIS)

Vanderveen, K.; Lutz, A.; Klebanoff, L.; Drennen, T.; Keller, J.; Drennen, T.; Kamery, W.

2006-01-01

The Hydrogen Futures Simulation Model (H 2 Sim) was used to project the cost for hydrogen at the point of sale to light duty vehicles for distributed, small-scale steam methane reforming. Projections cover the period from 2010-2050 in North America, and take into account assumptions about the quantity of recoverable natural gas remaining in North America. We conclude that there is a window for distributed reforming to play a positive role in supplying a H 2 fuel infrastructure, but this window is closing rapidly. The analysis assumes that production from natural gas reserves in North America will peak sometime before 2050 and demand will cause the price to rise after the peak of production in a manner consistent with Hotelling's model. We consider three scenarios for when the peak occurs, and evaluate the impact on the cost of hydrogen fuel produced via distributed small scale reforming in these three scenarios. (authors)

Thermodynamic modeling of the power plant based on the SOFC with internal steam reforming of methane

International Nuclear Information System (INIS)

Ivanov, Peter

2007-01-01

Mathematical model based on the thermodynamic modeling of gaseous mixtures is developed for SOFC with internal steam reforming of methane. Macroscopic porous-electrode theory, including non-linear kinetics and gas-phase diffusion, is used to calculate the reforming reaction and the concentration polarization. Provided the data concerning properties and costs of materials the model is fit for wide range of parametric analysis of thermodynamic cycles including SOFC

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

KAUST Repository

Takanabe, Kazuhiro; Basset, Jean-Marie; Park, Jung-Hyun; Samal, Akshaya Kumar; Alsabban, Bedour

2018-01-01

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

60-MW/sub t/ methanation plant design for HTGR process heat

International Nuclear Information System (INIS)

Davis, C.R.; Arcilla, N.T.; Hui, M.M.; Hutchins, B.A.

1982-07-01

This report describes a 60 MW(t) Methanation Plant for generating steam for industrial applications. The plant consists of four 15 MW(t) methanation trains. Each train is connected to a pipeline and receives synthesis gas (syngas) from a High Temperature Gas-Cooled Reactor Reforming (HTGR-R) plant. Conversion of the syngas to methane and water releases exothermic heat which is used to generate steam. Syngas is received at the Methanation Plant at a temperature of 80 0 F and 900 psia. One adiabatic catalytic reactor and one isothermal catalytic reactor, in each methanation train, converts the syngas to 92.2% (dry bases) methane. Methane and condensate are returned at temperatures of 100 to 125 0 F and at pressures of 860 to 870 psia to the HTGR-R plant for the reproduction of syngas

Modeling of electrochemistry and steam-methane reforming performance for simulating pressurized solid oxide fuel cell stacks

Energy Technology Data Exchange (ETDEWEB)

Recknagle, Kurtis P.; Ryan, Emily M.; Koeppel, Brian J.; Mahoney, Lenna A.; Khaleel, Moe A. [Pacific Northwest National Laboratory, Richland, WA 99352 (United States)

2010-10-01

This paper examines the electrochemical and direct internal steam-methane reforming performance of the solid oxide fuel cell when subjected to pressurization. Pressurized operation boosts the Nernst potential and decreases the activation polarization, both of which serve to increase cell voltage and power while lowering the heat load and operating temperature. A model considering the activation polarization in both the fuel and the air electrodes was adopted to address this effect on the electrochemical performance. The pressurized methane conversion kinetics and the increase in equilibrium methane concentration are considered in a new rate expression. The models were then applied in simulations to predict how the distributions of direct internal reforming rate, temperature, and current density are effected within stacks operating at elevated pressure. A generic 10 cm counter-flow stack model was created and used for the simulations of pressurized operation. The predictions showed improved thermal and electrical performance with increased operating pressure. The average and maximum cell temperatures decreased by 3% (20 C) while the cell voltage increased by 9% as the operating pressure was increased from 1 to 10 atm. (author)

Model-based analysis of CO2 revalorization for di-methyl ether synthesis driven by solar catalytic reforming

International Nuclear Information System (INIS)

Luu, Minh Tri; Milani, Dia; Sharma, Manish; Zeaiter, Joseph; Abbas, Ali

2016-01-01

Highlights: • Solar energy applied for synthesis of di-methyl ether via dry methane reforming. • Concentrated solar energy at receiver reaction zone for syngas generation. • H 2 /CO molar ratio of ‘1’ is maintained via two alternative processing routes. • Assessed three days of operation under different insolation levels. • Improvements of 18.7%, 32.2% and 20% for methane, energy and CO 2 emission intensities. - Abstract: The application of solar energy is investigated for the synthesis of di-methyl ether (DME) in a solar irradiated dry methane reformer (DMR). Solar radiations are concentrated onto a receiver and distributed to the reaction zone to provide necessary energy for syngas (CO and H 2 ) generation. In order to maintain a H 2 /CO molar ratio of ‘1’, as required in DME synthesis, the produced syngas is processed via two alternative routes: solar reformer coupled in parallel with a non-solar reformer (SoR-NSoR) and solar reformer integrated with a water-gas shift reactor (SoR-WGS). It is found that steam methane reforming (SMR) is the most suitable methodology when coupled with a solar reformer due to high H 2 content in the SMR syngas. Further performance analysis is conducted by simulating three days of operation under different insolation levels (high, medium and low irradiations). The simulation results showed that the SoR-WGS configuration produces the highest improvements of 18.7%, 32.2% and 20% in terms of methane, energy and CO 2 emission intensity respectively. This enhanced process performance originates from the exothermic nature of the WGS process which helps in controlling the overall syngas composition, whereas the SoR-NSoR requires fossil based thermal energy to drive the NSoR process to similar control targets. This promising improvement of all metrics in SoR-WGS may stimulate in-depth techno-economic feasibility of this unique solar integration for DME and other synthetic fuels production.

Catalytic dry reforming of waste plastics from different waste treatment plants for production of synthesis gases.

Science.gov (United States)

Saad, Juniza Md; Williams, Paul T

2016-12-01

Catalytic dry reforming of mixed waste plastics, from a range of different municipal, commercial and industrial sources, were processed in a two-stage fixed bed reactor. Pyrolysis of the plastics took place in the first stage and dry (CO 2 ) reforming of the evolved pyrolysis gases took place in the second stage in the presence of Ni/Al 2 O 3 and Ni-Co/Al 2 O 3 catalysts in order to improve the production of syngas from the dry reforming process. The results showed that the highest amount of syngas yield was obtained from the dry reforming of plastic waste from the agricultural industry with the Ni/Al 2 O 3 catalyst, producing 153.67mmol syngas g -1 waste . The addition of cobalt metal as a promoter to the Ni/Al 2 O 3 catalyst did not have a major influence on syngas yield. Overall, the catalytic-dry reforming of waste plastics from various waste treatment plants showed great potential towards the production of synthesis gases. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of methane steam reforming in planar porous support of solid oxide fuel cell

International Nuclear Information System (INIS)

Yang Yongping; Du Xiaoze; Yang Lijun; Huang Yuan; Xian Haizhen

2009-01-01

Adopting the porous support in integrated-planar solid oxide fuel cell (IP-SOFC) can reduce the operating temperature by reducing thickness of electrolyte layer, and also, provide internal reforming environment for hydrogen-rich fuel gas. The distributions of reactant and product components, and temperature of methane steam reforming for IP-SOFC were investigated by the developed physical and mathematical model with thermodynamic analysis, in which eleven possible reaction mechanisms were considered by the source terms and Arrhenius relationship. Numerical simulation of the model revealed that the progress of reforming reaction and the distribution of the product, H 2 , were influenced by the operating conditions, included that of temperature, ratio of H 2 O and CH 4 , as well as by the porosity of the supporting material. The simulating results indicate that the methane conversion rate can reach its maximum value under the operating temperature of 800 deg. C and porosity of ε = 0.4, which rather approximate to the practical operating conditions of IP-SOFC. In addition, characteristics of carbon deposition on surface of catalyst were discussed under various operating conditions and configuration parameters of the porous support. The present works provided some theoretical explanations to the numerous experimental observations and engineered practices

The role of promoters for Ni catalysts in low temperature (membrane) steam methane reforming

NARCIS (Netherlands)

Ligthart, D.A.J.M.; Pieterse, J.A.Z.; Hensen, E.J.M.

2011-01-01

In the search for active and stable Ni-based catalysts for steam methane reforming in membrane reactors, the effect of three different promoters La, B and Rh was compared. Promoted and unpromoted Ni catalysts were characterized by TEM, TPR and X-ray absorption spectroscopy. The average Ni particle

Thermochemical recuperative combined cycle with methane-steam reforming combustion; Tennengasu kaishitsu nensho ni yoru konbaindo saikuru hatsuden no kokoritsuka oyobi denryoku fuka heijunka taio

Energy Technology Data Exchange (ETDEWEB)

Kikuchi, R.; Essaki, K.; Tsutsumi, A. [The University of Tokyo, Tokyo (Japan). Dept. of Chemical System Engineering; Kaganoi, S.; Kurimura, H. [Teikoku Sekiyu Co., Tokyo (Japan); Sasaki, T.; Ogawa, T. [Toshiba Co., Tokyo (Japan)

2000-03-10

Thermochemical recuperative combined cycles with methane-steam reforming are proposed for improving their thermal efficiency and for peak-load leveling. For targeting higher thermal efficiency, a cycle with methane-steam reforming reaction heated by gas turbine exhaust was analyzed. The inlet temperature of gas turbine was set at 1,350 degree C. Low-pressure steam extracted from a steam turbine is mixed with methane, and then this mixture is heated by part of the gas turbine exhaust to promote a reforming reaction. The rest of the exhaust heat is used to produce steam, which drives steam turbines to generate electricity. The effect of steam-to-methane ratio (S/C) on thermal efficiency of the cycle, as well as on methane conversion, is investigated by using the ASPEN Plus process simulator. The methane feed rate was fixed at constant and S/C ratio was varied from 2.25 to 4.75. Methane conversion shows an increasing trend toward the ratio and has a maximum value of 17.9 % at S/C=4.0. Thermal efficiency for the system is about 51 % higher than that calculated for a conventional 1,300 degree C class combined cycle under similar conditions. A thermochemical recuperative combined cycle is designed for peak-load leveling. In night-time operation from 20 : 00 to 8 : 00 it stores hydrogen produced by methane steam reforming at S/C=3.9 to save power generation. The gas turbine inlet temperature is 1,330 degree C. In daytime operation from 8 : 00 to 20 : 00 the chemically recuperated combined cycle operated at S/C=2.0 is driven by the mixture of a combined cycle operated at constant load with the same methane feed rate, whereas daytime operation generated power 1.26 times larger than that of the combined cycle. (author)

Investigation of sulfur interactions on a conventional nickel-based solid oxide fuel cell anode during methane steam and dry reforming

Science.gov (United States)

Jablonski, Whitney S.

Solid oxide fuel cells (SOFC) are an attractive energy source because they do not have undesirable emissions, are scalable, and are feedstock flexible, which means they can operate using a variety of fuel mixtures containing H2 and hydrocarbons. In terms of fuel flexibility, most potential fuel sources contain sulfur species, which severely poison the nickel-based anode. The main objective of this thesis is to systematically evaluate sulfur interactions on a conventional Ni/YSZ anode and compare sulfur poisoning during methane steam and dry reforming (SMR and DMR) to a conventional catalyst (Sud Chemie, Ni/K2O-CaAl2O4). Reforming experiments (SMR and DMR) were carried out in a packed bed reactor (PBR), and it was demonstrated that Ni/YSZ is much more sensitive to sulfur poisoning than Ni/K2O-CaAl2O4 as evidenced by the decline in activity to zero in under an hour for both SMR and DMR. Adsorption and desorption of H2S and SO2 on both catalysts was evaluated, and despite the low amount of accessible nickel on Ni/YSZ (14 times lower than Ni/K2O-CaAl2O4), it adsorbs 20 times more H2S and 50 times more SO2 than Ni/K 2O-CaAl2O4. A one-dimensional, steady state PBR model (DetchemPBED) was used to evaluate SMR and DMR under poisoning conditions using the Deutschmann mechanism and a recently published sulfur sub-mechanism. To fit the observed deactivation in the presence of 1 ppm H2S, the adsorption/desorption equilibrium constant was increased by a factor 16,000 for Ni/YSZ and 96 for Ni/K2O-CaAl2O4. A tubular SAE reactor was designed and fabricated for evaluating DMR in a reactor that mimics an SOFC. Evidence of hydrogen diffusion through a supposedly impermeable layer indicated that the tubular SAE reactor has a major flaw in which gases diffuse to unintended parts of the tube. It was also found to be extremely susceptible to coking which leads to cell failure even in operating regions that mimic real biogas. These problems made it impossible to validate the tubular SAE

Optimization of a Pd-based membrane reactor for hydrogen production from methane steam reforming

Energy Technology Data Exchange (ETDEWEB)

Assis, A.J.; Hori, C.E.; Silva, L.C.; Murata, V.V. [Universidade Federal de Uberlandia (UFU), MG (Brazil). School of Chemical Engineering]. E-mail: adilsonjassis@gmail.com

2008-07-01

In this work, it is proposed a phenomenological model in steady state to describe the performance of a membrane reactor for hydrogen production through methane steam reform as well as it is performed an optimization of operating conditions. The model is composed by a set of ordinary differential equations from mass, energy and momentum balances and constitutive relations. They were used two different intrinsic kinetic expressions from literature. The results predicted by the model were validated using experimental data. They were investigated the effect of five important process parameters, inlet reactor pressure (PR0), methane feed flow rate (FCH40), sweep gas flow rate (FI), external reactor temperature (TW) and steam to methane feed flow ratio (M), both on methane conversion (XCH{sub 4} ) and hydrogen recovery (YH{sub 2}). The best operating conditions were obtained through simple parametric optimization and by a method based on gradient, which uses the computer code DIRCOL in FORTRAN. It is shown that high methane conversion (96%) as well as hydrogen recovery (91%) can be obtained, using the optimized conditions. (author)

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.

A novel integrated process of coal pyrolysis and methane CO{sub 2} reforming

Energy Technology Data Exchange (ETDEWEB)

Jing Wang; Pengfei Wang; Lijun Jin; Haoquan Hu [Dalian University of Technology, Dalian (China)

2007-07-01

In the paper, a novel pyrolysis method, namely coal pyrolysis coupling with CO{sub 2} reforming of methane (CRMP) or catalytic pyrolysis of coal coupling with CO{sub 2} reforming of methane (CRMCP), for improving the tar yield of coal pyrolysis was introduced. The behaviours of YM coal in both processes were investigated and compared with pyrolysis under N{sub 2} and H{sub 2}. The results show that the tar yield of coal pyrolysis in both processes obviously increase compared with that in N{sub 2} or H{sub 2}. When YM coal pyrolysis was carried out in stream of mixture gas CH{sub 4}/CO{sub 2} (1:1) with the existence of the catalyst at 0.1 MPa and 800{sup o}C, the tar yield is 2.8 times for CRMP and 4.3 times for CRMCP as that of pyrolysis under N{sub 2} and 1.7 and 2.6 times as that of hydropyrolysis at the same conditions, respectively. Sulfur content of char obtained from CRMP and CRMCP process are lower, especially in CRMP process, than that from N{sub 2} or H{sub 2}. 16 refs., 4 figs., 1 tab.

Energy efficient methane tri-reforming for synthesis gas production over highly coke resistant nanocrystalline Ni–ZrO_2 catalyst

International Nuclear Information System (INIS)

Singha, Rajib Kumar; Shukla, Astha; Yadav, Aditya; Adak, Shubhadeep; Iqbal, Zafar; Siddiqui, Nazia; Bal, Rajaram

2016-01-01

Highlights: • Tri-reforming of methane is an energy efficient process to produce synthesis gas. • Nanocrystalline Ni–ZrO_2 catalyst is prepared for tri-reforming of methane. • Strong metal-support interaction is the driving force for high activity. • The process produces synthesis gas with H_2/CO ratio of around 2. • The produced synthesis gas can be used to synthesize methanol. - Abstract: We report the synthesis of nanocrystalline Ni–ZrO_2 catalyst for tri-reforming of methane (5CH_4 + O_2 + CO_2 + 2H_2O → 6CO + 12H_2) to produce synthesis gas with H_2/CO mole ratio ∼2. Nanocrystalline Ni–ZrO_2 catalyst of size between 10 and 40 nm was prepared by hydrothermal method using cetyltrimethylammonium bromide (CTAB) as a surfactant. The prepared catalysts were characterized by N_2-physisorption studies, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature programmed reduction (TPR), H_2-chemisorpton, thermo-gravimetric analysis (TGA), Inductively coupled plasma atomic emission spectroscopy (ICP-AES) and X-ray photoelectron spectroscopy (XPS). The catalytic activity was monitored over temperature range between 500 and 800 °C. Different reaction parameters like temperature, Ni-loading, gas hourly space velocity (GHSV) and time on stream (TOS) were studied in detail. 4.8 wt% Ni loading for Ni–ZrO_2 catalyst was found to be the optimum Ni loading which showed the superior catalytic activity for methane tri-reforming. The catalyst was found to be stable for more than 100 h on time on stream with methane, carbon dioxide and steam conversion of ∼95% at 800 °C. The H_2/CO ratio was almost constant to 1.9 throughout the time on stream experiment. Highly dispersed nickel and the presence of strong metal support interaction were found to be the key factor for the superior activity of the catalyst. The effect of O_2 and H_2O concentration on reactant conversions and H_2/CO ratios were also

Sorption-enhanced steam methane reforming in fluidized bed reactors

Energy Technology Data Exchange (ETDEWEB)

Johnsen, Kim

2006-10-15

Hydrogen is considered to be an important potential energy carrier; however, its advantages are unlikely to be realized unless efficient means can be found to produce it without generation of CO{sub 2}. Sorption-enhanced steam methane reforming (SE-SMR) represent a novel, energy-efficient hydrogen production route with in situ CO{sub 2} capture, shifting the reforming and water gas shift reactions beyond their conventional thermodynamic limits. The use of fluidized bed reactors for SE-SMR has been investigated. Arctic dolomite, a calcium-based natural sorbent, was chosen as the primary CO{sub 2}-acceptor in this study due to high absorption capacity, relatively high reaction rate and low cost. An experimental investigation was conducted in a bubbling fluidized bed reactor of diameter 0.1 m, which was operated cyclically and batch wise, alternating between reforming/carbonation conditions and higher-temperature calcination conditions. Hydrogen concentrations of >98 mole% on a dry basis were reached at 600 C and 1 atm, for superficial gas velocities in the range of {approx}0.03-0.1 m/s. Multiple reforming-regeneration cycles showed that the hydrogen concentration remained at {approx}98 mole% after four cycles. The total production time was reduced with an increasing number of cycles due to loss of CO{sub 2}-uptake capacity of the dolomite, but the reaction rates of steam reforming and carbonation seemed to be unaffected for the conditions investigated. A modified shrinking core model was applied for deriving carbonation kinetics of Arctic dolomite, using experimental data from a novel thermo gravimetric reactor. An apparent activation energy of 32.6 kj/mole was found from parameter fitting, which is in good agreement with previous reported results. The derived rate expression was able to predict experimental conversion up to {approx}30% very well, whereas the prediction of higher conversion levels was poorer. However, the residence time of sorbent in a continuous

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

OpenAIRE

Ya-Li Du; Xu Wu; Qiang Cheng; Yan-Li Huang; Wei Huang

2017-01-01

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 r...

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...

Methane Steam Reforming over an Ni-YSZ Solid Oxide Fuel Cell Anode in Stack Configuration

DEFF Research Database (Denmark)

Mogensen, David; Grunwaldt, Jan-Dierk; Hendriksen, Peter Vang

2014-01-01

The kinetics of catalytic steam reforming of methane over an Ni-YSZ anode of a solid oxide fuel cell (SOFC) have been investigated with the cell placed in a stack configuration. In order to decrease the degree of conversion, a single cell stack with reduced area was used. Measurements were...

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

KAUST Repository

Blaylock, D. Wayne; Zhu, Yi-An; Green, William H.

2011-01-01

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

Low Temperature Steam Methane Reforming Over Ni Based Catalytic Membrane Prepared by Electroless Palladium Plating.

Science.gov (United States)

Lee, Sang Moon; Hong, Sung Chang; Kim, Sung Su

2018-09-01

A Pd/Ni-YSZ porous membrane with different palladium loadings and hydrazine as a reducing reagent was prepared by electroless plating and evaluated for the steam methane reforming activity. The steam-reforming activity of a Ni-YSZ porous membrane was greatly increased by the deposition of 4 g/L palladium in the low-temperature range (600 °C). With an increasing amount of reducing reagent, the Pd clusters were well dispersed on the Ni-YSZ surface and were uniform in size (∼500 nm). The Pd/Ni-YSZ catalytic porous membrane prepared by 1 of Pd/hydrazine ratio possessed an abundant amount of metallic Pd. The optimal palladium loadings and Pd/hydrazine ratio increased the catalytic activity in both the steam-reforming reaction and the Pd dispersion.

A novel and anti-agglomerating Ni@yolk–ZrO₂ structure with sub-10 nm Ni core for high performance steam reforming of methane

OpenAIRE

Lim, Zi-Yian; Wu, Chunzheng; Wang, Wei Guo; Choy, Kwang-Leong; Yin, Hongfeng

2015-01-01

Steam reforming of methane is a versatile technology for hydrogen production in oil refinery and fuel cell applications. Using natural gas is a promising method to produce rich-hydrogen gas. Ni@yolk–ZrO₂ catalyst is used to study steam reforming of methane under various GHSVs, steam-to-carbon (S/C) ratio, and its recyclability. The catalyst was characterized using a combination of XRD, TEM, AAS, TPR, TPH, TGA, BET, XPS, and Raman techniques. The catalyst is evaluated on time stream and identi...

Thermophilic Dry Methane Fermentation of Distillation Residue Eluted from Ethanol Fermentation of Kitchen Waste and Dynamics of Microbial Communities.

Science.gov (United States)

Huang, Yu-Lian; Tan, Li; Wang, Ting-Ting; Sun, Zhao-Yong; Tang, Yue-Qin; Kida, Kenji

2017-01-01

Thermophilic dry methane fermentation is advantageous for feedstock with high solid content. Distillation residue with 65.1 % moisture content was eluted from ethanol fermentation of kitchen waste and subjected to thermophilic dry methane fermentation, after adjusting the moisture content to 75 %. The effect of carbon to nitrogen (C/N) ratio on thermophilic dry methane fermentation was investigated. Results showed that thermophilic dry methane fermentation could not be stably performed for >10 weeks at a C/N ratio of 12.6 and a volatile total solid (VTS) loading rate of 1 g/kg sludge/d; however, it was stably performed at a C/N ratio of 19.8 and a VTS loading rate of 3 g/kg sludge/d with 83.4 % energy recovery efficiency. Quantitative PCR analysis revealed that the number of bacteria and archaea decreased by two orders of magnitude at a C/N ratio of 12.6, whereas they were not influenced at a C/N ratio of 19.8. Microbial community analysis revealed that the relative abundance of protein-degrading bacteria increased and that of organic acid-oxidizing bacteria and acetic acid-oxidizing bacteria decreased at a C/N ratio of 12.6. Therefore, there was accumulation of NH 4 + and acetic acid, which inhibited thermophilic dry methane fermentation.

Low CO2-emissions hybrid solar combined-cycle power system with methane membrane reforming

International Nuclear Information System (INIS)

Li, Yuanyuan; Zhang, Na; Cai, Ruixian

2013-01-01

Based on the principle of cascade utilization of multiple energy resources, a gas-steam combined cycle power system integrated with solar thermo-chemical fuel conversion and CO 2 capture has been proposed and analyzed. The collected solar heat at 550 °C drives the endothermic methane reforming and is converted to the produced syngas chemical exergy, and then released as high-temperature thermal energy via combustion for power generation, achieving its high-efficiency heat-power conversion. The reforming reaction is integrated with a hydrogen separation membrane, which continuously withdraws hydrogen from the reaction zone and enables nearly full methane conversion. The CO 2 enriched gas being concentrated in the retentate zone is collected and processed with pre-combustion decarbonization. The system is thermodynamically simulated using the ASPEN PLUS code. The results show that with 91% CO 2 captured, the specific CO 2 emission is 25 g/kWh. An exergy efficiency of 58% and thermal efficiency of 51.6% can be obtained. A fossil fuel saving ratio of 31.2% is achievable with a solar thermal share of 28.2%, and the net solar-to-electricity efficiency based on the gross solar heat incident on the collector is about 36.4% compared with the same gas-steam combined cycle system with an equal CO 2 removal ratio obtained by post-combustion decarbonization. - Highlights: ► A solar-assisted hybrid combined cycle power system has been proposed and analyzed. ► The system integrates power generation with solar-driven reforming and CO 2 capture. ► solar heat upgrading and high-efficiency heat-to-power conversion are achieved. ► membrane reforming enables high CH 4 conversion and pre-combustion CO 2 capture. ► The system thermodynamic performances have been investigated and compared

Process for manufacture of a catalyst suitable for the steam reforming of hydrocarbons and for obtaining methane

Energy Technology Data Exchange (ETDEWEB)

Golebiowski, A.; Romotowski, T.; Hennel, W.; Wroblewska-Wroblewska, T.; Polanski, A.; Janecki, Z.; Paluch-Paluch, S.

1982-07-29

The invention concerns a process for the manufacture of a catalyst suitable for the steam reforming of hydrocarbons or for obtaining methane, by the deposition of the catalytic components on a metal carrier with a large surface area, particularly a process for the manufacture of a solid nickel catalyst, which is suitable for the steam reforming of hydrocarbons, particularly of methane. The following steps of the process are carried out: producing a highly porous layer of spongy metal from Ni powder on the side of a metal wall away from a heat medium, which separates the reaction mixture from the heat medium, then separate application of a non-reducing oxide (Al/sub 2/O/sub 3/) and a reducing oxide (nickel oxide) on the spongy metal by soaking with metal salt solution and then roasting in the temperature range of 400 to 1200/sup 0/C.

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

The influence of calcination temperature on catalytic activities in a Co based catalyst for CO2 dry reforming

International Nuclear Information System (INIS)

Song, Sang-Hoon; Son, Ju-Hee; Budiman, Anatta Wahyu; Choi, Myoung-Jae; Chang, Tae-Sun; Shin, Chae-Ho

2014-01-01

The carbon dioxide dry reforming of methane (CDR) reaction could be thermodynamically favored in the range of 800 to 1,000 .deg. C. However, the catalyst in this reaction should be avoided at the calcination temperature over 800 .deg. C since strong metal support interaction (SMSI) in this temperature range can decrease activity due to loss of active sites. Therefore, we focused on optimizing the temperature of pretreatment and a comparison of surface characterization results for CDR. Results related to metal sintering over support, re-dispersion by changing of particle size of metal-support, and strong metal support interaction were observed and confirmed in this work. In our conclusion, optimum calcination temperature for a preparation of catalyst was proposed that 400 .deg. C showed a higher and more stable catalytic activity without changing of support characteristics

Two-dimensional thermal analysis of radial heat transfer of monoliths in small-scale steam methane reforming

DEFF Research Database (Denmark)

Cui, Xiaoti; Kær, Søren Knudsen

2018-01-01

Monolithic catalysts have received increasing attention for application in the small-scale steam methane reforming process. The radial heat transfer behaviors of monolith reformers were analyzed by two-dimensional computational fluid dynamic (CFD) modeling. A parameter study was conducted...... by a large number of simulations focusing on the thermal conductivity of the monolith substrate, washcoat layer, wall gap, radiation heat transfer and the geometric parameters (cell density, porosity and diameter of monolith). The effective radial thermal conductivity of the monolith structure, kr......,eff, showed good agreement with predictions made by the pseudo-continuous symmetric model. This influence of the radiation heat transfer is low for highly conductive monoliths. A simplified model has been developed to evaluate the importance of radiation for monolithic reformers under different conditions...

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

KAUST Repository

Zhou, Lu; Guo, Yu; Kameyama, Hideo; Basset, Jean-Marie

2014-01-01

. 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

On direct internal methane steam reforming kinetics in operating solid oxide fuel cells with nickel-ceria anodes

Science.gov (United States)

Thallam Thattai, A.; van Biert, L.; Aravind, P. V.

2017-12-01

Major operating challenges remain to safely operate methane fuelled solid oxide fuel cells due to undesirable temperature gradients across the porous anode and carbon deposition. This article presents an experimental study on methane steam reforming (MSR) global kinetics for single operating SOFCs with Ni-GDC (gadolinium doped ceria) anodes for low steam to carbon (S/C) ratios and moderate current densities. The study points out the hitherto insufficient research on MSR global and intrinsic kinetics for operating SOFCs with complete Ni-ceria anodes. Further, it emphasizes the need to develop readily applicable global kinetic models as a subsequent step from previously reported state-of-art and complex intrinsic models. Two rate expressions of the Power law (PL) and Langmuir-Hinshelwood (LH) type have been compared and based on the analysis, limitations of using previously proposed rate expressions for Ni catalytic beds to study MSR kinetics for complete cermet anodes have been identified. Firstly, it has been shown that methane reforming on metallic (Ni) current collectors may not be always negligible, contrary to literature reports. Both PL and LH kinetic models predict significantly different local MSR reaction rate and species partial pressure distributions along the normalized reactor length, indicating a strong need for further experimental verifications.

Influences of doping Cr/Fe/Ta on the performance of Ni/CeO{sub 2} catalyst under microwave irradiation in dry reforming of CH{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Odedairo, Taiwo [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia); Ma, Jun [School of Engineering, University of South Australia, Mawson Lakes, SA (Australia); Chen, Jiuling, E-mail: cjlchen@yahoo.com [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia); Wang, Shaobin [Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia); Zhu, Zhonghua, E-mail: z.zhu@uq.edu.au [School of Chemical Engineering, The University of Queensland, St Lucia, Brisbane (Australia)

2016-01-15

The structure of Ni/CeO{sub 2} catalyst with doping of Cr, Fe and Ta was investigated with XRD, N{sub 2} physisorption, XPS and HRTEM and the catalytic activity of the catalysts under microwave irradiation in dry reforming of methane was tested in a microwave reactor. The results show that the introduction of Cr and Ta to Ni/CeO{sub 2} can enhance the interaction between Ni and the support/promoter and inhibit the enlargement of NiO particles during the synthesis. The CH{sub 4} conversions in dry reforming on the catalysts follow the order: Ni/CeO{sub 2}<2Fe–Ni<2Ta–Ni<2Cr–Ni. The superior performance of 2Ta–Ni and 2Cr–Ni may be attributed to the locally-heated Ni particles caused by the strong microwave absorption of the in-situ grown graphene attached on them under microwave irradiation. - Highlights: • The influences of doping Cr, Fe and Ta on Ni/CeO{sub 2} were investigated. • The catalytic performances before and after doping were investigated. • The in-situ grown graphene can promote the conversion of reactants.

HIGHTEX: a computer program for the steady-state simulation of steam-methane reformers used in a nuclear process heat plant

International Nuclear Information System (INIS)

Tadokoro, Yoshihiro; Seya, Toko

1977-08-01

This report describes a computational model and the input procedure of HIGHTEX, a computer program for steady-state simulation of the steam-methane reformers used in a nuclear process heat plant. The HIGHTEX program simulates rapidly a single reformer tube, and treats the reactant single-phase in the two-dimensional catalyst bed. Output of the computer program is radial distributions of temperature and reaction products in the catalyst-packed bed, pressure loss of the packed bed, stress in the reformer tube, hydrogen permeation rate through the reformer tube, heat rate of reaction, and heat-transfer rate between helium and process gas. The running time (cpu) for a 9m-long bayonet type reformer tube is 12 min with FACOM-230/75. (auth.)

In silico search for novel methane steam reforming catalysts

International Nuclear Information System (INIS)

Xu, Yue; Lausche, Adam C; Khan, Tuhin S; Abild-Pedersen, Frank; Studt, Felix; Nørskov, Jens K; Bligaard, Thomas; 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 ‘CatApp’) 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 metal alloy catalysts. (paper)

Thermodynamic analysis of direct internal reforming of methane and butane in proton and oxygen conducting fuel cells

NARCIS (Netherlands)

Biesheuvel, P.M.; Geerlings, J.J.C.

2008-01-01

We present results of a thermodynamic analysis of direct internal reforming fuel cells, based on either a proton conducting fuel cell (FC-H+) or an oxygen ion conducting fuel cell (FC-O2-). We analyze the option of methane as fuel as well as butane. The model self-consistently combines all chemical

Preliminary risk analysis of an Hydrogen production plant using the reformed process of methane with vapor coupled to a high temperature nuclear reactor

International Nuclear Information System (INIS)

Flores y Flores, A.; Nelson E, P.F.; Francois L, J.L.

2004-01-01

It is necessary to identify the different types of dangers, as well as their causes, probabilities and consequences of the same ones, inside plants, industries and any process to classify the risks. This work is focused in particular to a study using the technical HAZOP (Hazard and Operability) for a plant of reformed of methane with vapor coupled to a nuclear reactor of the type HTTR (High Temperature Test Reactor), which is designed to be built in Japan. In particular in this study the interaction is analyzed between the nuclear reactor and the plant of reformed of methane with vapor. After knowing the possible causes of risk one it is built chart of results of HAZOP to have a better vision of the consequences of this faults toward the buildings and constructions, to people and the influence of the fault on each plant; for what there are proposed solutions to mitigate these consequences or to avoid them. The work is divided in three sections: a brief introduction about the technique of HAZOP; some important aspects of the plant of reformed of methane with vapor; and the construction of the chart of results of HAZOP. (Author)

Utilizing methane from degassing as a fuel for furnaces of drying systems. [USSR

Energy Technology Data Exchange (ETDEWEB)

Matveev, V.I.; Telegin, A.K.

1984-10-01

The use is evaluated of methane from coal seam degassing in the Severnaya mine as a fuel for dryers in the Severnaya coal preparation plant in the USSR. Dryers used in the plant are equipped with PMZ-4TsR furnaces. Middlings (type Zh18 coal) with 30% ash content and 0.25 MJ/kg calorific value were used as a fuel. When dryers were fired with middlings moisture content in coal concentrate declined from 10.1% to 5.1%, system output amounted to 133 t/h. After plant modernization middlings were replaced with methane from coal seam degassing (methane content in the mixture with air ranged from 40 to 60%). Replacing middlings with methane increased dryer output from 133 to 203 t/h. Moisture content in dried coal was reduced from 11.8 to 4.8%. Repair cost decreased, environmental pollution caused by combustion also declined. Payback period amounted to 6 months.

Methane Steam Reforming over an Ni-YSZ Solid Oxide Fuel Cell Anode in Stack Configuration

Directory of Open Access Journals (Sweden)

D. Mogensen

2014-01-01

Full Text Available The kinetics of catalytic steam reforming of methane over an Ni-YSZ anode of a solid oxide fuel cell (SOFC have been investigated with the cell placed in a stack configuration. In order to decrease the degree of conversion, a single cell stack with reduced area was used. Measurements were performed in the temperature range 600–800°C and the partial pressures of all reactants and products were varied. The obtained rates could be well fitted with a power law expression (r ∝PCH40.7. A simple model is presented which is capable of predicting the methane conversion in a stack configuration from intrinsic kinetics of the anode support material. The predictions are compared with the stack measurements presented here, and good agreement is observed.

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.

Hydrogen Production via Glycerol Dry Reforming over La-Ni/Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Kah Weng Siew

2013-12-01

Full Text Available Glycerol (a bio-waste generated from biodiesel production has been touted as a promising bio-syngas precursor via reforming route. Previous studies have indicated that carbon deposition is the major performance-limiting factor for nickel (Ni catalyst during glycerol steam reforming. In the current paper, dry (CO2-reforming of glycerol, a new reforming route was carried out over alumina (Al2O3-supported non-promoted and lanthanum-promoted Ni catalysts. Both sets of catalysts were synthesized via wet co-impregnation procedure. The physicochemical characterization of the catalyst showed that the promoted catalyst possessed smaller metal crystallite size, hence higher metal dispersion compared to the virgin Ni/Al2O3 catalyst. This was also corroborated by the surface images captured by the FESEM analysis. In addition, BET surface area measurement gave 92.05m²/g for non-promoted Ni catalyst whilst promoted catalysts showed an average of 1 to 6% improvement depending on the La loading. Reaction studies at 873 K showed that glycerol dry reforming successfully produced H2 with glycerol conversion and H2 yield that peaked at 9.7% and 25% respectively over 2wt% La content. The optimum catalytic performance by 2%La-Ni/Al2O3 can be attributed to the larger BET surface area and smaller crystallite size that ensured accessibility of active catalytic sites.  © 2013 BCREC UNDIP. All rights reservedReceived: 12nd May 2013; Revised: 7th October 2013; Accepted: 16th October 2013[How to Cite: Siew, K.W., Lee, H.C., Gimbun, J., Cheng, C.K. (2013. Hydrogen Production via Glycerol Dry Reforming over La-Ni/Al2O3 Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 160-166. (doi:10.9767/bcrec.8.2.4874.160-166][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4874.160-166

Refurbished dry methane on catalysts Ni / BaTiO 1x In x o 3d

International Nuclear Information System (INIS)

Garcia, Veronica; Caldes, Maria T; Joubert Olivier

2008-01-01

The effect of the support on the catalytic performance of Ni catalysts in carbon dioxide reforming of methane was studied using perovskite based supports BaTi 1x In x O 3d, known by their ionic and electronic conductivity properties. The results of the investigation showed that there is a close relationship between the catalytic activity and the reducibility of the support.

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

Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

Science.gov (United States)

Porosoff, Marc D; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Chen, Jingguang G

2015-12-14

The recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2 ) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2 ). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2 C-based materials preserve the CC bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Circulating fluidized bed reformer-regenerator system for hydrogen production from methane. Paper no. IGEC-1-092

International Nuclear Information System (INIS)

Prasad, P.; Elnashaie, S.S.E.H.

2005-01-01

Steam reforming is presently the principal route for large-scale hydrogen production from natural gas. This paper proposes a novel concept of a reactor-regenerator type circulating fluidized bed (Prasad and Elnashaie, 2002) for efficient production of hydrogen. Carbon is optimally allowed to form on the catalyst in the reactor section through methane cracking and Boudouard coking reactions, and the deactivated catalyst is regenerated in the regenerator by burning off the carbon. This concept of carbon formation and burning cannot be used in a fixed bed configuration but is possible in the proposed novel Circulating Fluidized Bed (CFB) configuration, which employs a reactor-regenerator type of configuration. Allowing both carbon formation and steam reforming to occur simultaneously by introducing steam as part of the feed, gives more than 3 moles hydrogen per mole of methane at almost zero energy consumption. The steam can be fed as water at room temperature, and the hot catalyst returning from the regenerator can be used to vaporize it into steam. This route is the most efficient from both hydrogen yield and energy consumption points of view. This CFB configuration exhibits the bifurcation behavior and the present paper reports an investigation of its static bifurcation characteristics through a rigorous mathematical model. (author)

Hydrogen production through sorption-enhanced steam methane reforming and membrane technology: A review

International Nuclear Information System (INIS)

Barelli, L.; Bidini, G.; Gallorini, F.; Servili, S.

2008-01-01

With the rapid development of industry, more and more waste gases are emitted into the atmosphere. In terms of total air emissions, CO 2 is emitted in the greatest amount, accounting for 99 wt% of the total air emissions, therefore contributing to global warming, the so-called 'Greenhouse Effect'. The recovery and disposal of CO 2 from flue gas is currently the object of great international interest. Most of the CO 2 comes from the combustion of fossil fuels in power generation, industrial boilers, residential and commercial heating, and transportation sectors. Consequently, in the last years' interest in hydrogen as an energy carrier has significantly increased both for vehicle fuelling and stationary energy production from fuel cells. The benefits of a hydrogen energy policy are the reduction of the greenhouse effect, principally due to the centralization of the emission sources. Moreover, an improvement to the environmental benefits can be achieved if hydrogen is produced from renewable sources, as biomass. The present paper provides an overview of the steam methane reforming (SMR) process and methodologies for performances improvement such as hydrogen removal, by selective permeation through a membrane or simultaneous reaction of the targeted molecule with a chemical acceptor, and equilibrium shift by the addition of a CO 2 acceptor to the reactor. In particular, attention was focused on the sorption-enhanced steam methane reforming (SE-SMR) process in which sorbents are added in order to enhance the reactions and realize in situ CO 2 separation. The major operating parameters of SE-SMR are described by the authors in order to project and then realize the innovative carbonation reactor developed in previous studies

Numerical analysis of hydrogen production via methane steam reforming in porous media solar thermochemical reactor using concentrated solar irradiation as heat source

International Nuclear Information System (INIS)

Wang, Fuqiang; Tan, Jianyu; Shuai, Yong; Gong, Liang; Tan, Heping

2014-01-01

Highlights: • H 2 production by hybrid solar energy and methane steam reforming is analyzed. • MCRT and FVM coupling method is used for chemical reaction in solar porous reactor. • LTNE model is used to study the solid phase and fluid phase thermal performance. • Modified P1 approximation programmed by UDFs is used for irradiative heat transfer. - Abstract: The calorific value of syngas can be greatly upgraded during the methane steam reforming process by using concentrated solar energy as heat source. In this study, the Monte Carlo Ray Tracing (MCRT) and Finite Volume Method (FVM) coupling method is developed to investigate the hydrogen production performance via methane steam reforming in porous media solar thermochemical reactor which includes the mass, momentum, energy and irradiative transfer equations as well as chemical reaction kinetics. The local thermal non-equilibrium (LTNE) model is used to provide more temperature information. The modified P1 approximation is adopted for solving the irradiative heat transfer equation. The MCRT method is used to calculate the sunlight concentration and transmission problems. The fluid phase energy equation and transport equations are solved by Fluent software. The solid phase energy equation, irradiative transfer equation and chemical reaction kinetics are programmed by user defined functions (UDFs). The numerical results indicate that concentrated solar irradiation on the fluid entrance surface of solar chemical reactor is highly uneven, and temperature distribution has significant influence on hydrogen production

High temperature ceramic-tubed reformer

Science.gov (United States)

Williams, Joseph J.; Rosenberg, Robert A.; McDonough, Lane J.

1990-03-01

The overall objective of the HiPHES project is to develop an advanced high-pressure heat exchanger for a convective steam/methane reformer. The HiPHES steam/methane reformer is a convective, shell and tube type, catalytic reactor. The use of ceramic tubes will allow reaction temperature higher than the current state-of-the-art outlet temperatures of about 1600 F using metal tubes. Higher reaction temperatures increase feedstock conversion to synthesis gas and reduce energy requirements compared to currently available radiant-box type reformers using metal tubes. Reforming of natural gas is the principal method used to produce synthesis gas (primarily hydrogen and carbon monoxide, H2 and CO) which is used to produce hydrogen (for refinery upgrading), methanol, as well as several other important materials. The HiPHES reformer development is an extension of Stone and Webster's efforts to develop a metal-tubed convective reformer integrated with a gas turbine cycle.

Coke-free dry reforming of model diesel fuel by a pulsed spark plasma at low temperatures using an exhaust gas recirculation (EGR) system

Energy Technology Data Exchange (ETDEWEB)

Sekine, Yasushi; Furukawa, Naotsugu; Matsukata, Masahiko; Kikuchi, Eiichi, E-mail: ysekine@waseda.jp [Department of Applied Chemistry, Waseda University, 65-301, Okubo, Shinjuku, Tokyo 169-8555 (Japan)

2011-07-13

Dry reforming of diesel fuel, an endothermic reaction, is an attractive process for on-board hydrogen/syngas production to increase energy efficiency. For operating this dry reforming process in a vehicle, we can use the exhaust gas from an exhaust gas recirculation (EGR) system as a source of carbon dioxide. Catalytic dry reforming of heavy hydrocarbon is a very difficult reaction due to the high accumulation of carbon on the catalyst. Therefore, we attempted to use a non-equilibrium pulsed plasma for the dry reforming of model diesel fuel without a catalyst. We investigated dry reforming of model diesel fuel (n-dodecane) with a low-energy pulsed spark plasma, which is a kind of non-equilibrium plasma at a low temperature of 523 K. Through the reaction, we were able to obtain syngas (hydrogen and carbon monoxide) and a small amount of C{sub 2} hydrocarbon without coke formation at a ratio of CO{sub 2}/C{sub fuel} = 1.5 or higher. The reaction can be conducted at very low temperatures such as 523 K. Therefore, it is anticipated as a novel and effective process for on-board syngas production from diesel fuel using an EGR system.

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

KAUST Repository

Reddy Enakonda, Linga; Zhou, Lu; Saih, Youssef; Ould-Chikh, Samy; Lopatin, Sergei; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

2016-01-01

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

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.

Energy-efficient biogas reforming process to produce syngas: The enhanced methane conversion by O_2

International Nuclear Information System (INIS)

Chen, Xuejing; Jiang, Jianguo; Li, Kaimin; Tian, Sicong; Yan, Feng

2017-01-01

Highlights: • The effect of O_2 content from 0 to 15% on Ni/SiO_2 are studied for biogas reforming. • The presence of O_2 in biogas improves CH_4 conversion and stability of biogas reforming. • An obvious carbon-resistance effect is observed due to the carbon gasification effect of O_2 in biogas. • The presence of O_2 in biogas greatly helps inhibit the catalyst sintering. - Abstract: We report an energy-efficient biogas reforming process with high and stable methane conversions by O_2 presence. During this biogas reforming process, the effects of various O_2 concentrations in biogas on initial conversions and stability at various temperatures on a Ni/SiO_2 catalyst were detailed investigated. In addition, theoretical energy consumption and conversions were calculated based on the Gibbs energy minimization method to compare with experimental results. Carbon formation and sintering during the reforming process were characterized by thermal gravity analysis, the Brunauer-Emmett-Teller method, X-ray diffraction, and high-resolution transmission electron microscopy to investigate the feasibility of applying this process to an inexpensive nickel catalyst. The results showed that 5% O_2 in biogas improved the CH_4 conversion and stability of biogas reforming. The enhancement of stability was attributed to the inhibited sintering, our first finding, and the reduced carbon deposition at the same time, which sustained a stable conversion of CH_4, and proved the applicability of base Ni catalyst to this process. Higher O_2 concentrations (⩾10%) in biogas resulted in severe decrease in CO_2 conversion and greater H_2O productivity. Our proposed biogas reforming process, with a high and stable conversion of CH_4, reduced energy input, and the applicability to inexpensive base metal catalyst, offers a good choice for biogas reforming with low O_2 concentrations (⩽5%) to produce syngas with high energy efficiency.

Demonstration of direct internal reforming for MCFC power plants

Energy Technology Data Exchange (ETDEWEB)

Aasberg-Petersen, K.; Christensen, P.S.; Winther, S.K. [HALDOR TOPSOE A/S, Lynby (Denmark)] [and others

1996-12-31

The conversion of methane into hydrogen for an MCFC by steam reforming is accomplished either externally or internally in the stack. In the case of external reforming the plant electrical efficiency is 5% abs. lower mainly because more parasitic power is required for air compression for stack cooling. Furthermore, heat produced in the stack must be transferred to the external reformer to drive the endothermic steam reforming reaction giving a more complex plant lay-out. A more suitable and cost effective approach is to use internal steam reforming of methane. Internal reforming may be accomplished either by Indirect Internal Reforming (DIR) and Direct Internal Reforming (DIR) in series or by DIR-only as illustrated. To avoid carbon formation in the anode compartment higher hydrocarbons in the feedstock are converted into hydrogen, methane and carbon oxides by reaction with steam in ail adiabatic prereformer upstream the fuel cell stack. This paper discusses key elements of the desire of both types of internal reforming and presents data from pilot plants with a combined total of more than 10,000 operating hours. The project is being carried out as part of the activities of the European MCFC Consortium ARGE.

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.

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.

The Effect of WO3 Modification of ZrO2 Support on the Ni-Catalyzed Dry Reforming of Biogas Reaction for Syngas Production

Directory of Open Access Journals (Sweden)

Nikolaos D. Charisiou

2017-10-01

Full Text Available The time-on-stream catalytic performance and stability of 8 wt. % Ni catalyst supported on two commercially available catalytic supports, ZrO2 and 15 wt.% WO3-ZrO2, was investigated under the biogas dry reforming reaction for syngas production, at 750°C and a biogas quality equal to CH4/CO2 = 1.5, that represents a common concentration of real biogas. A number of analytical techniques such as N2 adsorption/desorption (BET method, XRD, H2-TPR, NH3- and CO2-TPD, SEM, ICP, thermal analysis (TGA/DTG and Raman spectroscopy were used in order to determine textural, structural and other physicochemical properties of the catalytic materials, and the type of carbon deposited on the catalytic surface of spent samples. These techniques were used in an attempt to understand better the effects of WO3-induced modifications on the catalyst morphology, physicochemical properties and catalytic performance. Although Ni dispersion and reducibility characteristics were found superior on the modified Ni/WZr sample than that on Ni/Zr, its dry reforming of methane (DRM performance was inferior; a result attributed to the enhanced acidity and complete loss of the basicity recorded on this catalyst, an effect that competes and finally overshadows the benefits of the other superior properties. Raman studies revealed that the degree of graphitization decreases with the insertion of WO3 in the crystalline structure of the ZrO2 support, as the ID/IG peak intensity ratio is 1.03 for the Ni/Zr and 1.29 for the Ni/WZr catalyst.

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

Science.gov (United States)

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.

Preparation and characterization of {alpha}-AI{sub 2}O{sub 3} catalytic supports. Application to methane steam reforming; Preparation et caracterisation de supports catalytiques d`Al{sub 2}O{sub 3} {alpha}. Application au vaporeformange du methane

Energy Technology Data Exchange (ETDEWEB)

Marturano, M.A.; Ferretti, O.A. [Centro de Investigacion y Desarrollo en Procesos Cataliticas (CINDECA), La Plata (Argentina); Aglietti, E.F. [Centro de Tecnologia de Recursos Minerales y Ceramica (CETMIC, UNPL and CONICET), (Argentina)

1995-12-31

{alpha}Al{sub 2}O{sub 3} preformed bodies are widely used as catalytic supports in many industrial processes as for instance steam reforming. In this work, is particularly studied the textural, structural, morphological and mechanical properties of {alpha}-Al{sub 2}O{sub 3} supports as a function of the characteristics of the starting alumina and of the bonding agents used. The performance of these supports in the final catalyst in methane steam reforming is also studies. It was found that textural and morphological properties are determined only by the starting alumina utilized in support preparation. When non-stabilized alumina powders are used (small grains), mechanical properties of the support are controlled by the sintering process, independently of the binder used. When stabilized alumina powders are used (large grains) the existence of ceramic and chemical bonds leads to better results (bentonite and mono-aluminium phosphate, BM supports). Materials with adequate catalytic properties in methane steam reforming can be obtained when using supports prepared from powders easily found (commercial raw alumina) 20 refs.

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.

Experimental and Numerical Study of Low Temperature Methane Steam Reforming for Hydrogen Production

Directory of Open Access Journals (Sweden)

Martin Khzouz

2017-12-01

Full Text Available Low temperature methane steam reforming for hydrogen production, using experimental developed Ni/Al2O3 catalysts is studied both experimentally and numerically. The catalytic activity measurements were performed at a temperature range of 500–700 °C with steam to carbon ratio (S/C of 2 and 3 under atmospheric pressure conditions. A mathematical analysis to evaluate the reaction feasibility at all different conditions that have been applied by using chemical equilibrium with applications (CEA software and in addition, a mathematical model focused on the kinetics and the thermodynamics of the reforming reaction is introduced and applied using a commercial finite element analysis software (COMSOL Multiphysics 5.0. The experimental results were employed to validate the extracted simulation data based on the yields of the produced H2, CO2 and CO at different temperatures. A maximum hydrogen yield of 2.7 mol/mol-CH4 is achieved at 700 °C and S/C of 2 and 3. The stability of the 10%Ni/Al2O3 catalyst shows that the catalyst is prone to deactivation as supported by Thermogravimetric Analysis TGA results.

The effects of climate changes on soil methane oxidation in a dry Arctic tundra

Science.gov (United States)

D'Imperio, Ludovica

2014-05-01

The effects of climate changes on soil methane oxidation in a dry Arctic tundra. Ludovica D'Imperio1, Anders Michelsen1, Christian J. Jørgensen1, Bo Elberling1 1Center for Permafrost (CENPERM), Department of Geosciences and Natural Resource Management, University of Copenhagen, Denmark At Northern latitudes climatic changes are predicted to be most pronounced resulting in increasing active layer depth and changes in growing season length, vegetation cover and nutrient cycling. As a consequence of increased temperature, large stocks of carbon stored in the permafrost-affected soils could become available for microbial transformations and under anoxic conditions result in increasing methane production affecting net methane (CH4) budget. Arctic tundra soils also serves as an important sink of atmospheric CH4 by microbial oxidation under aerobic conditions. While several process studies have documented the mechanisms behind both production and emissions of CH4 in arctic ecosystems, an important knowledge gap exists with respect to the in situ dynamics of microbial-driven uptake of CH4 in arctic dry lands which may be enhanced as a consequence of global warming and thereby counterbalancing CH4 emissions from Arctic wetlands. In-situ methane measurements were made in a dry Arctic tundra in Disko Island, Western Greenland, during the summer 2013 to assess the role of seasonal and inter-annual variations in temperatures and snow cover. The experimental set-up included snow fences installed in 2012, allowed investigations of the emissions of GHGs from soil under increased winter snow deposition and ambient field conditions. The soil fluxes of CH4 and CO2 were measured using closed chambers in manipulated plots with increased summer temperatures and shrub removal with or without increased winter precipitation. At the control plots, the averaged seasonal CH4 oxidation rates ranged between -0.05 mg CH4 m-2 hr-1 (end of August) and -0.32 mg CH4 m-2 hr-1 (end of June). In the

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)

Performance evaluation and comparison of fuel processors integrated with PEM fuel cell based on steam or autothermal reforming and on CO preferential oxidation or selective methanation

International Nuclear Information System (INIS)

Ercolino, Giuliana; Ashraf, Muhammad A.; Specchia, Vito; Specchia, Stefania

2015-01-01

Highlights: • Modeling of different fuel processors integrated with PEM fuel cell stack. • Steam or autothermal reforming + CO selective methanation or preferential oxidation. • Reforming of different hydrocarbons: gasoline, light diesel oil, natural gas. • 5 kW e net systems comparison via energy efficiency and primary fuel rate consumed. • Highest net efficiency: steam reformer + CO selective methanation based system. - Abstract: The performances of four different auxiliary power unit (APU) schemes, based on a 5 kW e net proton exchange membrane fuel cell (PEM-FC) stack, are evaluated and compared. The fuel processor section of each APU is characterized by a reformer (autothermal ATR or steam SR), a non-isothermal water gas shift (NI-WGS) reactor and a final syngas catalytic clean-up step: the CO preferential oxidation (PROX) reactor or the CO selective methanation (SMET) one. Furthermore, three hydrocarbon fuels, the most commonly found in service stations (gasoline, light diesel oil and natural gas) are considered as primary fuels. The comparison is carried out examining the results obtained by a series of steady-state system simulations in Aspen Plus® of the four different APU schemes by varying the fed fuel. From the calculated data, the performance of CO-PROX is not very different compared to that of the CO-SMET, but the performance of the SR based APUs is higher than the scheme of the ATR based APUs. The most promising APU scheme with respect to an overall performance target is the scheme fed with natural gas and characterized by a fuel processor chain consisting of SR, NI-WGS and CO-SMET reactors. This processing reactors scheme together with the fuel cell section, notwithstanding having practically the same energy efficiency of the scheme with SR, NI-WGS and CO-PROX reactors, ensures a less complex scheme, higher hydrogen concentration in the syngas, lower air mass rate consumption, the absence of nitrogen in the syngas and higher potential

Method of preparing a catalyst suitable for steam reformation of hydrocarbons and for methane production. [German patent

Energy Technology Data Exchange (ETDEWEB)

Golebiowski, A; Romotowski, T; Hennel, W; Wroblewska-Wroblewska, T; Polanski, A; Janecki, Z; Paluch-Paluch, S

1977-05-26

A method of producing a nickel catalyst suitable for steam reformation and methane production is described which forms a permanent bond with the inner surface of an externally heated metal tube, e.g. a heat exchanger tube. To begin with, a metal sponge with good adhesion to the metal tube is produced on the basis of a metallic powder of the metal group which is treated by a conventional calcination process. The metal sponge is then covered with a metal oxide which is not reduced under reformation conditions, e.g. aluminium oxide, by wetting the metal sponge with aluminium nitrate and repeated calcination. Wetting and calcination are repeated twice, and the calcination temperature is lower each time in the range between 400 and 1200/sup 0/C. The activated nickel is there deposited by wetting with a nickel salt solution and subsequent calcination.

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.

Controlled deposition and utilization of carbon on Ni-YSZ anodes of SOFCs operating on dry methane

International Nuclear Information System (INIS)

Jiao, Yong; Zhang, Liqin; An, Wenting; Zhou, Wei; Sha, Yujing; Shao, Zongping; Bai, Jianping; Li, Si-Dian

2016-01-01

Solid oxide fuel cells (SOFCs) are promising power-generation systems to utilize methane or methane-based fuels with a high energy efficiency and low environmental impact. A successive multi-stage process is performed to explore the operation of cells using dry methane or the deposited carbon from methane decomposition as fuel. Stable operation can be maintained by optimizing the fuel supply and current density parameters. An electrochemical impedance analysis suggests that the partial oxidization of Ni can occur at anodes when the carbon fuel is consumed. The stability of cells operated on pure methane is investigated in three operating modes. The cell can run in a comparatively stable state with continuous power output in an intermittent methane supply mode, where the deposition and utilization of carbon is controlled by balancing the fuel supply and consumption. The increase in the polarization resistance of the cell might originate from the small amount of NiO and residual carbon at the anode, which can be removed via an oxidation-and-reduction maintenance process. Based on the above strategy, this work provides an alternative operating mode to improve the stability of direct methane SOFCs and demonstrates the feasibility of its application. - Highlights: • A new strategy to control the deposition and utilization of carbon was developed. • A stable fuel cell operation was obtained with an intermittent fuel supply mode. • Polarization resistance increased due to small amount of NiO and residual carbon.

High accuracy measurements of dry mole fractions of carbon dioxide and methane in humid air

Science.gov (United States)

Rella, C. W.; Chen, H.; Andrews, A. E.; Filges, A.; Gerbig, C.; Hatakka, J.; Karion, A.; Miles, N. L.; Richardson, S. J.; Steinbacher, M.; Sweeney, C.; Wastine, B.; Zellweger, C.

2013-03-01

Traditional techniques for measuring the mole fractions of greenhouse gases in the well-mixed atmosphere have required dry sample gas streams (dew point < -25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmosphere Watch programme of the World Meteorological Organisation (WMO/GAW) for carbon dioxide (±0.1 ppm in the Northern Hemisphere and ±0.05 ppm in the Southern Hemisphere) and methane (±2 ppb). Drying the sample gas to low levels of water vapour can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular cavity ring down spectroscopy, have led to the development of greenhouse gas analysers capable of simultaneous measurements of carbon dioxide, methane and water vapour. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapour, these instruments permit accurate and precise greenhouse gas measurements that can meet the WMO/GAW inter-laboratory compatibility goals (WMO, 2011a) without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapour correction factors, and we summarise a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterised dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to a water vapour concentration of at least 1%. By determining the correction factors for individual instruments once at the start of life, this water vapour concentration range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended up to and even above 4% water vapour concentrations.

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.

OXIDATIVE-REFORMING OF METHANE AND PARTIAL OXIDATION OF METHANE REACTIONS OVER NiO/PrO2/ZrO2 CATALYSTS: EFFECT OF NICKEL CONTENT

Directory of Open Access Journals (Sweden)

Y. J. O. Asencios

Full Text Available Abstract In this work the behavior of NiO-PrO2-ZrO2 catalysts containing various nickel loadings was evaluated in the partial oxidation of methane and oxidative-reforming reactions of methane. The catalysts were characterized by X-Ray Diffraction Analysis (in situ-XRD, Temperature Programmed Reduction (H2-TPR, Scanning Electron Microscopy (SEM/EDX and Adsorption-Desorption of nitrogen (BET area. The reactions were carried out at 750 °C and 1 atm for 5 hours. The catalysts were studied with different nickel content: 0, 5, 10 and 15% (related to total weight of catalyst, wt%. In both reactions, the catalyst containing the mixture of the three oxides (NiO/PrO2/ZrO2 with 15% nickel (15NiPrZr catalyst showed the best activity for the conversion of the reactants into Syngas and showed high selectivity for H2 and CO. The results suggest that the promoter PrO2 and the Niº centers are in a good proportion in the catalyst with 15% Ni. Our results showed that low nickel concentrations in the catalyst led to high metallic dispersion; however, very low nickel concentrations did not favor the methane transformation into Syngas. The catalyst containing only NiO/ZrO2 in the mixture was not sufficient for the catalysis. The presence of the promoter PrO2 was very important for the catalysis of the POM.

The application of inelastic neutron scattering to investigate the steam reforming of methane over an alumina-supported nickel catalyst

International Nuclear Information System (INIS)

McFarlane, Andrew R.; Silverwood, Ian P.; Norris, Elizabeth L.; Ormerod, R. Mark; Frost, Christopher D.; Parker, Stewart F.; Lennon, David

2013-01-01

Highlights: • Inelastic neutron scattering has been used to investigate a Ni/alumina catalyst. • The extent of hydrogen retention by the catalyst has been determined. • Filamentous carbon is identified as a by-product. - Abstract: An alumina-supported nickel catalyst, previously used in methane reforming experiments employing CO 2 as the oxidant, is applied here in the steam reforming variant of the process. Micro-reactor experiments are used to discern an operational window compatible with sample cells designed for inelastic neutron scattering (INS) experiments. INS spectra are recorded after 6 h reaction of a 1:1 mixture of CH 4 and H 2 O at 898 K. Weak INS spectra are observed, indicating minimal hydrogen retention by the catalyst in this operational regime. Post-reaction, the catalyst is further characterised by powder X-ray diffraction, transmission electron microscopy and Raman scattering. In a comparable fashion to that seen for the ‘dry’ reforming experiments, the catalyst retains substantial quantities of carbon in the form of filamentous coke. The role for hydrogen incorporation by the catalyst is briefly considered

The application of inelastic neutron scattering to investigate the steam reforming of methane over an alumina-supported nickel catalyst

Energy Technology Data Exchange (ETDEWEB)

McFarlane, Andrew R.; Silverwood, Ian P. [School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ (United Kingdom); Norris, Elizabeth L.; Ormerod, R. Mark [Department of Chemistry, School of Physical and Geographical Sciences, Keele University, Staffs ST5 5BG (United Kingdom); Frost, Christopher D.; Parker, Stewart F. [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); Lennon, David, E-mail: David.Lennon@glasgow.ac.uk [School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ (United Kingdom)

2013-12-12

Highlights: • Inelastic neutron scattering has been used to investigate a Ni/alumina catalyst. • The extent of hydrogen retention by the catalyst has been determined. • Filamentous carbon is identified as a by-product. - Abstract: An alumina-supported nickel catalyst, previously used in methane reforming experiments employing CO{sub 2} as the oxidant, is applied here in the steam reforming variant of the process. Micro-reactor experiments are used to discern an operational window compatible with sample cells designed for inelastic neutron scattering (INS) experiments. INS spectra are recorded after 6 h reaction of a 1:1 mixture of CH{sub 4} and H{sub 2}O at 898 K. Weak INS spectra are observed, indicating minimal hydrogen retention by the catalyst in this operational regime. Post-reaction, the catalyst is further characterised by powder X-ray diffraction, transmission electron microscopy and Raman scattering. In a comparable fashion to that seen for the ‘dry’ reforming experiments, the catalyst retains substantial quantities of carbon in the form of filamentous coke. The role for hydrogen incorporation by the catalyst is briefly considered.

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.

Plasma devices for hydrocarbon reformation

KAUST Repository

Cha, Min Suk

2017-02-16

Plasma devices for hydrocarbon reformation are provided. Methods of using the devices for hydrocarbon reformation are also provided. The devices can include a liquid container to receive a hydrocarbon source, and a plasma torch configured to be submerged in the liquid. The plasma plume from the plasma torch can cause reformation of the hydrocarbon. The device can use a variety of plasma torches that can be arranged in a variety of positions in the liquid container. The devices can be used for the reformation of gaseous hydrocarbons and/or liquid hydrocarbons. The reformation can produce methane, lower hydrocarbons, higher hydrocarbons, hydrogen gas, water, carbon dioxide, carbon monoxide, or a combination thereof.

Preparation and characterization of a nickel/alumina composite membrane for high temperature hydrogen separation. Application in a membrane reactor for the dry reforming of methane; De la synthese d'une membrane composite nikel/ceramique permselective a l'hydrogene au reacteur membranaire. Application au reformage du methane

Energy Technology Data Exchange (ETDEWEB)

Haag, St.

2003-11-01

The objective of this work was to develop composite inorganic membranes based on nickel or palladium supported on a porous ceramic for high temperature hydrogen separation. These membranes were used in a membrane reactor for the dry reforming of methane in order to shift the chemical equilibrium towards the production of hydrogen and carbon monoxide. The metal layers were deposited on a tubular alumina support by electroless plating. The Ni and the Pd layers are 1 micron thick. The hydrogen permeation tests were done for high temperatures. The Pd/ceramic membrane is permselective to hydrogen and the H{sub 2}/N{sub 2} separation factor (single gas) is 60 at 400 deg C with a transmembrane pressure difference of 1 bar. With a gas mixture, the H{sub 2}/N{sub 2} separation factor is 13. This membrane is not completely dense and the transport mechanism of hydrogen through the Pd layer is mixed: solution-diffusion through the metal bulk and surface diffusion through the defects of the film. However, an embrittlement of the palladium layer under hydrogen atmosphere was observed at 500 deg C. The Ni/ceramic membrane is stable until 600 deg C, its permselectivity to hydrogen increases with the temperature. The use of a sweep gas can provide a H{sub 2}/N{sub 2} separation factor (mixture) of about 25. The main diffusion mechanism is surface diffusion through the pores. Both membranes are not catalytic. Thus, some catalysts composed of nickel and cobalt supported on MgO, SiO{sub 2} or Al{sub 2}O{sub 3} were prepared. These systems allow to reach theoretical limits of conversion calculated for a conventional fixed bed reactor. In the membrane reactor, an enhancement of the methane conversion (15-20%) is observed with both membranes due the selective removal of hydrogen during the reaction. The Ni/ceramic membrane more stable, more permeable and as selective as the palladium one is a brand new material for high temperature hydrogen separation. (author)

Carbon dioxide reforming of methane by atmospheric pressure pulsed glow discharge: The effect of pulse compression

International Nuclear Information System (INIS)

Ghorbanzadeh, A.; Modarresi, H.

2006-01-01

Methane reforming by carbon dioxide in atmospheric pressure pulsed glow discharge was examined. The pulse duration of plasma was compressed to ∼50 ns or lower. This compression allowed working at higher frequencies, more than 3 k Hz, without glow to arc transition. The main outlet gases were synthetic gases (H 2 , CO) and C 2 (ethylene, ethane, and acetylene) products. At equal reactants proportion CO 2 /CH 4 =1, about 42 p ercent o f plasma energy went to chemical dissociation while reactant conversions were relatively high, i.e. near 55 p ercent % (CH 4 ) and 42 p ercent ( CO 2 ). At this point, the energy expenditure was less than 3.8 eV per each converted molecule. The reactor energy performance even gets better at higher CO 2 /CH 4 proportions. At CO 2 /CH 4 =5, The conversions of about 65 p ercent a nd 45 p ercent w ere obtained for methane and carbon dioxide respectively, while energy efficiency reached near 45 p ercent . It is discussed that high nonequilibrium state of vibrational energy at short pulses, especially in carbon dioxide, leads to this improvement.

Hydrogen production from steam methane reforming and electrolysis as part of a near-term hydrogen infrastructure

International Nuclear Information System (INIS)

Roberts, K.

2003-01-01

Building a complete hydrogen infrastructure for a transportation system based on Fuel Cells (FC) and hydrogen is a risky and expensive ordeal, especially given that it is not known with complete certainty that Fuel Cells will indeed replace the gasoline ICE. But how can we expect the diffusion of an automotive technology if there is no infrastructure to support its fuel needs? This gives rise to a chicken and egg type problem. One way to get around this problem is to produce hydrogen when and where it is needed. This solves the problems of high costs associated with expensive pipeline distribution networks, the high energy-intensities associated with liquefaction of hydrogen and the high costs of cryogenic equipment. This paper will consider the advantages and disadvantages of two such hydrogen production mechanisms, namely, onsite production of hydrogen from Electrolysis and onsite production of hydrogen from Steam Methane Reforming (SMR). Although SMR hydrogen may be more economical due to the availability and low cost of methane, under certain market and technological conditions onsite electrolytic hydrogen can be more attractive. The paper analyses the final price of delivered hydrogen based on its sensitivity to market conditions and technology developments. (author)

Coupling and reforming of methane by means of low pressure radio-frequency plasmas

Energy Technology Data Exchange (ETDEWEB)

Pedro Patino; Yasnahir Perez; Manuel Caetano [Universidad Central de Venezuela, Caracas (Venezuela). Escuela de Quimica, Facultad de Ciencias

2005-11-01

Non-oxidative coupling of CH{sub 4}/H{sub 2} mixtures was carried out by means of radio frequency (rf) glow discharges for the first time. A central composite design was employed to determine the best experimental conditions for methane transformation into higher hydrocarbons and to fit the experimental data. RF power was the factor showing the highest effect on the results while CH{sub 4}/H{sub 2} mole ratio showed the lowest. Conversion was 46.4% at 100 W, 0.07 mbar and CH{sub 4}/H{sub 2} mole ratio of . Selectivity was 56.9% for C{sub 2}, 6.9% for C{sub 3}, and 36.2% for C{sub 4} hydrocarbons. Least squares fits of quadratic equations yielded approximating functions permitting to predict results of random experiments with errors of about 5%. The same rf system was used for the reforming of methane with CO{sub 2}, O{sub 2}, and steam plasmas, respectively. The highest oxidation was observed with oxygen whilst steam plasma produced the best results. H{sub 2}/CO mole ratio was adjusted by setting specific experimental parameters of the latter. CO{sub 2} free synthesis gas was produced at higher H{sub 2}O and CH{sub 4} flow rates, i.e. 0.8 mmol/h and higher power, i.e. 100 W. CO{sub 2} and CO free H{sub 2} was produced at 0.3 and 0.6 mmol/h flow rates of H{sub 2}O and CH{sub 4}, respectively, and 50 W. 26 refs., 3 figs., 6 tabs.

Internal reforming of methane in a mono-block-layer build solid oxide fuel cell with an embedding porous pipe: Numerical analysis

International Nuclear Information System (INIS)

Ramírez-Minguela, J.J.; Mendoza-Miranda, J.M.; Muñoz-Carpio, V.D.; Rangel-Hernández, V.H.; Pérez-García, V.; Rodríguez-Muñoz, J.L.

2014-01-01

Highlights: • A MOLB-type SOFC with different biogas compositions is modeled. • Internal reforming of methane and water gas shift in the anode side are considered. • Changes in the SOFC according to the phenomena inside of them are assessed. • A new configuration for the MOLB-type geometry is proposed. • Temperature gradients effects in the new configuration are significant. - Abstract: A mono-block-layer build type (MOLB-type) geometry, composed with trapezoidal cross-section channels for fuel and air, of solid oxide fuel cell (SOFC), is modeled in this study using a three dimensional computational fluid dynamics (CFD). The model is used to obtain the performance of the SOFC considering internal reforming of methane in the anode side with different biogas compositions. From the results obtained, a new configuration for the MOLB-type geometry is proposed. The model takes into account the mass transfer, heat transfer, species transport, chemical and electrochemical reactions, detailed comparisons of species concentration, temperature and electric fields inside the cell analyzed in the present study. Results show that the biogas from local sludge has the lower temperature gradient and more homogeneous current density distributions along of the fuel cell, on the other hand, with the new configuration proposed for the MOLB-type geometry the temperature distribution inside of the fuel cell has lower temperature gradients

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)

In-situ study of the gas-phase composition and temperature of an intermediate-temperature solid oxide fuel cell anode surface fed by reformate natural gas

Science.gov (United States)

Santoni, F.; Silva Mosqueda, D. M.; Pumiglia, D.; Viceconti, E.; Conti, B.; Boigues Muñoz, C.; Bosio, B.; Ulgiati, S.; McPhail, S. J.

2017-12-01

An innovative experimental setup is used for in-depth and in-operando characterization of solid oxide fuel cell anodic processes. This work focuses on the heterogeneous reactions taking place on a 121 cm2 anode-supported cell (ASC) running with a H2, CH4, CO2, CO and steam gas mixture as a fuel, using an operating temperature of 923 K. The results have been obtained by analyzing the gas composition and temperature profiles along the anode surface in different conditions: open circuit voltage (OCV) and under two different current densities, 165 mA cm-2 and 330 mA cm-2, corresponding to 27% and 54% of fuel utilization, respectively. The gas composition and temperature analysis results are consistent, allowing to monitor the evolution of the principal chemical and electrochemical reactions along the anode surface. A possible competition between CO2 and H2O in methane internal reforming is shown under OCV condition and low current density values, leading to two different types of methane reforming: Steam Reforming and Dry Reforming. Under a current load of 40 A, the dominance of exothermic reactions leads to a more marked increase of temperature in the portion of the cell close to the inlet revealing that current density is not uniform along the anode surface.

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

DEFF Research Database (Denmark)

Kehres, Jan

/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......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...... range from 298 - 1023 K. Correlated crystallite and particle growth due to sintering were observed after the decomposition of the surfactant. Furthermore transformations from rod to spherical particle shape were observed. In situ reduction experiments of a Ni/MgAl2O4 catalyst were performed. The Ni...

Syngas production from ethanol dry reforming over Rh/CeO2 catalyst

Directory of Open Access Journals (Sweden)

Shulin Zhao

2018-01-01

Full Text Available Carbon dioxide reforming of ethanol over Rh/CeO2 catalyst was deeply investigated at different reaction temperatures of 450–700 °C and reactant ratios (CO2/ethanol from 1 to 3 under atmospheric pressure. The obtained results indicated that Rh/CeO2 catalyst presented a promising activity and stability for syngas production from renewable bio-ethanol instead of conventional methane. Typically, CO2-rich conditions (CO2/ethanol = 3 were favorable for reaction process and dynamic coke cleaning, which led to remarkably stable performance over 65 h on stream. The strong redox capacity of CeO2 support might also accelerate CO2 activation and prevent the carbon accumulation over the catalyst surface. Additionally, tunable H2/CO ratios were available by changing the CO2/ethanol ratios. The results from characterization of samples before and after catalytic tests allowed to establish the relationship between textural properties and catalytic performance.

MethaneSat: Detecting Methane Emissions in the Barnett Shale Region

Science.gov (United States)

Propp, A. M.; Benmergui, J. S.; Turner, A. J.; Wofsy, S. C.

2017-12-01

In this study, we investigate the new information that will be provided by MethaneSat, a proposed satellite that will measure the total column dry-air mole fraction of methane at 1x1 km or 2x2 km spatial resolution with 0.1-0.2% random error. We run an atmospheric model to simulate MethaneSat's ability to characterize methane emissions from the Barnett Shale, a natural gas province in Texas. For comparison, we perform observation system simulation experiments (OSSEs) for MethaneSat, the National Oceanic and Atmospheric administration (NOAA) surface and aircraft network, and Greenhouse Gases Observing Satellite (GOSAT). The results demonstrate the added benefit that MethaneSat would provide in our efforts to monitor and report methane emissions. We find that MethaneSat successfully quantifies total methane emissions in the region, as well as their spatial distribution and steep gradients. Under the same test conditions, both the NOAA network and GOSAT fail to capture this information. Furthermore, we find that the results for MethaneSat depend far less on the prior emission estimate than do those for the other observing systems, demonstrating the benefit of high sampling density. The results suggest that MethaneSat would be an incredibly useful tool for obtaining detailed methane emission information from oil and gas provinces around the world.

Biogas and Methane Yield from Rye Grass

Directory of Open Access Journals (Sweden)

Tomáš Vítěz

2015-01-01

Full Text Available Biogas production in the Czech Republic has expanded substantially, including marginal regions for maize cultivation. Therefore, there are increasingly sought materials that could partially replace maize silage, as a basic feedstock, while secure both biogas production and its quality.Two samples of rye grass (Lolium multiflorum var. westerwoldicum silage with different solids content 21% and 15% were measured for biogas and methane yield. Rye grass silage with solid content of 15% reached an average specific biogas yield 0.431 m3·kg−1 of organic dry matter and an average specific methane yield 0.249 m3·kg−1 of organic dry matter. Rye grass silage with solid content 21% reached an average specific biogas yield 0.654 m3·kg−1 of organic dry matter and an average specific methane yield 0.399 m3·kg−1 of organic dry matter.

Design of a nuclear steam reforming plant

International Nuclear Information System (INIS)

Malherbe, J.

1980-01-01

The design of a plant for the steam reforming of methane using a High Temperature Reactor has been studied by CEA in connection with the G.E.G.N. This group of companies (CEA, GAZ DE FRANCE, CHARBONNAGES DE FRANCE, CREUSOT-LOIRE, NOVATOME) is in charge of studying the feasibility of the coal gasification process by using a nuclear reactor. The process is based on the hydrogenation of the coal in liquid phase with hydrogen produced by a methane steam reformer. The reformer plant is fed by a pipe of natural gas or SNG. The produced hydrogen feeds the gasification plant which could not be located on the same site. An intermediate hydrogen storage between the two plants could make the coupling more flexible. The gasification plant does not need a great deal of heat and this heat can be satisfied mostly by internal heat exchanges

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.

Reforming technology for syngas production

International Nuclear Information System (INIS)

Epstein, M.

1997-01-01

Methane forming reactions using either steam or CO 2 have been known to industry for a long time. These endothermic reactions require the investment of a relatively large amount of energy. German researchers, in the 1970's, conceived and developed the idea to use this reaction and the reverse methanation reaction in a closed loop for the transportation and distribution of nuclear heat. The idea was also adopted for use with solar energy as a heat source. Utilizing solar energy as the heat source, the Weismann Institute of Science has fabricated, installed and operated a complete loop capable of the conversion and transportation of over 400 kW of heat. This system can be operated with a wide range of CO 2 /H 2 O/CH 4 feed mixtures. Steam reforming is the common reforming reaction in the ''open loop'' mode for the purpose of synthesis gas production. This is accomplished with a large excess of steam on a nickel catalyst. However, it has only recently been recognized that there is also a substantial market for CO 2 reforming. The CO 2 /CH 4 mixture in various proportions exists in many places and has, so far, not been used efficiently. The sources for this mixture are biogas produced in anaerobic digestion processes and gas resources such as the NATUNA gas field in Indonesia, and many others. Therefore, the system of CO 2 /CH 4 deserves more attention. Commercial catalysts used for steam reforming based on nickel are not suitable for this system. Therefore, other catalysts based on Rhodium and Ruthenium have been developed and some performance data is presented in this paper. Also presented is a conceptual schematic layout of a CO 2 reforming plant and matching methanator. A computer code for a detailed design of the entire loop in a commercial size system has been prepared where optimized operational conditions as well as equipment parameters can be determined. (author). 3 figs, 3 tabs

Dry reforming of coke oven gases over activated carbon to produce syngas for methanol synthesis

Energy Technology Data Exchange (ETDEWEB)

J.M. Bermudez; B. Fidalgo; A. Arenillas; J.A. Menendez [Instituto Nacional del Carbn, Oviedo (Spain)

2010-10-15

The dry reforming of coke oven gases (COG) over an activated carbon used as catalyst has been studied in order to produce a syngas suitable for methanol synthesis. The primary aim of this work was to study the influence of the high amount of hydrogen present in the COG on the process of dry reforming, as well as the influence of other operation conditions, such us temperature and volumetric hourly space velocity (VHSV). It was found that the reverse water gas shift (RWGS) reaction takes place due to the hydrogen present in the COG, and that its influence on the process increases as the temperature decreases. This situation may give rise to the consumption of the hydrogen present in the COG, and the consequent formation of a syngas which is inappropriate for the synthesis of methanol. This reaction can be avoided by working at high temperatures (about 1000{sup o}C) in order to produce a syngas that is suitable for methanol synthesis. It was also found that the RWGS reaction is favoured by an increase in the VHSV. In addition, the active carbon FY5 was proven to be an adequate catalyst for the production of syngas from COG. 25 refs., 7 figs., 2 tabs.

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)

Modeling Plasma-based CO2 and CH4 Conversion in Mixtures with N2, O2 and H2O: the Bigger Plasma Chemistry Picture

KAUST Repository

Wang, Weizong; Snoeckx, Ramses; Zhang, Xuming; Cha, Min; Bogaerts, Annemie

2018-01-01

performed regarding the single component gases, i.e. CO2 splitting and CH4 reforming, as well as for two component mixtures, i.e. dry reforming of methane (CO2/CH4), partial oxidation of methane (CH4/O2), artificial photosynthesis (CO2/H2O), CO2

Biomass estimates, characteristics, biochemical methane potential, kinetics and energy flow from Jatropha curcus on dry lands

Energy Technology Data Exchange (ETDEWEB)

Nallathambi Gunaseelan, V. [Department of Zoology, PSG College of Arts and Science, Coimbatore 641 014 (India)

2009-04-15

In this study, we examined the production of Jatropha curcus plants on 1 ha of rain fed dry lands. All of the plant components that would result from plantation tending, fruit harvesting and processing were sampled for their yield and chemical composition, and then subjected to the biochemical methane potential (BMP) assay. The component parts exhibited significant variation in BMP which was reflected in their ultimate methane yield which ranged from 0.08 to 0.97 L g{sup -1} VS added, and their first order kinetics which ranged from 0.07 to 0.14 d{sup -1}. We examined two integrated utilization schemes: the first which converted plant prunings, fruit hulls and de-oiled seed cake to methane, and the oil to fatty acid methyl-ester (FAME); the second was to convert the seeds, plant prunings and fruit hulls entirely to methane. The basis for the plantation was, a density of 4444 plant ha{sup -1} (1.5 m x 1.5 m spacing), with a seed yield of 0.911 kg TS plant{sup -1} (1 kg total weight) with an oil content of 35% providing an annual oil yield of 1.42 t y{sup -1}. The corresponding yields of pruned leaves, fruit hulls and de-oiled cake are 0.97, 1.0, and 2.35 t VS ha y{sup -1}, respectively. An integrated scheme of producing biogas by means of anaerobic digestion of the latter components and oil for biodiesel would produce 90 GJ ha{sup -1} y{sup -1} in total with the oil being 54 GJ. The alternative biogas only option which would convert the seed oil into methane instead of biodiesel would produce 97 GJ ha{sup -1} y{sup -1}. (author)

Carbon Dioxide Dry Reforming of Glycerol for Hydrogen Production using Ni/ZrO2 and Ni/CaO as Catalysts

Directory of Open Access Journals (Sweden)

Nur Nabillah Mohd Arif

2016-08-01

Full Text Available Glycerol, byproduct from the biodiesel production can be effectively utilized as the promising source of synthesis gas (syngas through a dry reforming reaction. Combination of these waste materials with greenhouse gases which is carbon dioxide (CO2 will help to reduce environmental problem such as global warming. This dry reforming reaction has been carried out in a fixed bed batch reactor at 700 °C under the atmospheric pressure for 3 hours. In this experiment, reforming reaction was carried out using Nickel (Ni as based catalyst and supported with zirconium (ZrO2 and calcium (CaO oxides. The catalysts were prepared by wet impregnation method and characterized using Bruanaer-Emmett-Teller (BET surface area, Scanning Electron Microscopy (SEM, X-ray Diffraction (XRD, Thermo Gravimetric (TGA, and Temperature Programmed Reduction (TPR analysis. Reaction studies show that 15% Ni/CaO give the highest hydrogen yield and glycerol conversion that peaked at 24.59% and 30.32%, respectively. This result is verified by XRD analysis where this catalyst shows low crystallinity and fine dispersion of Ni species resulted in high specific surface area which gives 44.93 m2/g that is validated by BET.  Copyright © 2016 BCREC GROUP. All rights reserved Received: 21st January 2016; Revised: 24th February 2016; Accepted: 29th February 2016 How to Cite: Arif, N.M.M., Vo, D.V.N., Azizan,M.T., Abidin S.Z. (2016. Carbon Dioxide Dry Reforming of Glycerol for Hydrogen Production using Ni/ZrO2 and Ni/CaO as Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 200-209 (doi:10.9767/bcrec.11.2.551.200-209 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.551.200-209

Stability, carbon resistance, and reactivity toward autothermal reforming of nickel on ceria-based supports

International Nuclear Information System (INIS)

Sutthisripok, W.; Laosiripojana, N.

2004-01-01

'Full text:' Solid Oxide Fuel Cell (SOFC) normally requires a reformer unit, where the fuel such as natural gas, methane, methanol, or ethanol can be reformed to hydrogen before introducing to the main part of fuel cell. Nickel on commercial supports such as Al2O3, MgO, ZrO2 has been widely reported to be used as the reforming catalyst commercially. Carbon formation and catalyst deactivation are always the main problems of using this type of catalyst. It is well established that CeO2 and CeO2-ZrO2 have been applied as the catalysts in a wide variety of reactions involving oxidation or partial oxidation of hydrocarbons (e.g. automotive catalysis). In order to quantify the performance of nickel on CeO2 and CeO2-ZrO2 supports for reformer application, the stabilities toward methane steam reforming and the carbon formation resistance were studied. After 18 hours, nickel on CeO2-ZrO2 with the Ce/Zr ratio of 3/1 presented the best performance in term of stability and activity. It also provided excellent resistance toward carbon formation compared to commercial Ni/Al2O3. The autothermal reforming of methane over Ni catalyst on CeO2 and CeO2-ZrO2 supports were also investigated. Ni/Ce-ZrO2 with the Ce/ Zr ratio of 3/1 also showed the best performance. The kinetics of this reaction was also studied. In the temperature range of 750-900C, the reaction order in methane was always closed to 1. The catalyst showed a slight positive effect of hydrogen and a negative effect of steam on the steam reforming rate. The addition of oxygen increased the steam reforming rate. However, the productions of CO and H2 decreased with increasing oxygen partial pressure. (author)

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; Laveille, Paco; Anjum, Dalaver H.; Caps, Valerie; Basset, Jean-Marie

2015-01-01

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

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

Inquiry on the valorisation of heat produced by methanization with co-generation in France. Energy and territory: Valorisation of heat produced by methanization

International Nuclear Information System (INIS)

Bazin, Florian; David, Laura; Heuraux, Thalie; Jeziorny, Thibaud; Massazza, Michael; Mosse, Noemie; Nguyen Dai, Kim Yen; Pruvost, Paul; Regimbart, Amelie; Rogee, Pierre-Emmanuel; Roy, Samuel; Segret, Emilien

2014-01-01

A leaflet first proposes graphs which illustrate the valorisation of heat produced by methanization with co-generation in France: material and methods, farm characterisation, plant sources, valorisation modes. The second document proposes detailed and discussed presentations of the various involved processes. Contributions address methanization as a whole, valorisation of heat produced by co-generation through heating of agricultural and domestic buildings or through digestate dehydration, digestate hygienisation, and other types of valorisation such as fodder drying, cereal drying, wood drying, compost drying, fabrication of rape seed, greenhouse crops, cultures of micro algae, and mushroom farming

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.)

Highly Dispersed Nickel-Containing Mesoporous Silica with Superior Stability in Carbon Dioxide Reforming of Methane: The Effect of Anchoring

Directory of Open Access Journals (Sweden)

Wenjia Cai

2014-03-01

Full Text Available A series of nickel-containing mesoporous silica samples (Ni-SiO2 with different nickel content (3.1%–13.2% were synthesized by the evaporation-induced self-assembly method. Their catalytic activity was tested in carbon dioxide reforming of methane. The characterization results revealed that the catalysts, e.g., 6.7%Ni-SiO2, with highly dispersed small nickel particles, exhibited excellent catalytic activity and long-term stability. The metallic nickel particle size was significantly affected by the metal anchoring effect between metallic nickel particles and unreduced nickel ions in the silica matrix. A strong anchoring effect was suggested to account for the remaining of small Ni particle size and the improved catalytic performance.

Steam reforming of fuel to hydrogen in fuel cells

Science.gov (United States)

Fraioli, Anthony V.; Young, John E.

1984-01-01

A fuel cell capable of utilizing a hydrocarbon such as methane as fuel and having an internal dual catalyst system within the anode zone, the dual catalyst system including an anode catalyst supporting and in heat conducting relationship with a reforming catalyst with heat for the reforming reaction being supplied by the reaction at the anode catalyst.

Hydrogen Production from Cyclic Chemical Looping Steam Methane Reforming over Yttrium Promoted Ni/SBA-16 Oxygen Carrier

Directory of Open Access Journals (Sweden)

Sanaz Daneshmand-Jahromi

2017-09-01

Full Text Available In this work, the modification of Ni/SBA-16 oxygen carrier (OC with yttrium promoter is investigated. The yttrium promoted Ni-based oxygen carrier was synthesized via co-impregnation method and applied in chemical looping steam methane reforming (CL-SMR process, which is used for the production of clean energy carrier. The reaction temperature (500–750 °C, Y loading (2.5–7.4 wt. %, steam/carbon molar ratio (1–5, Ni loading (10–30 wt. % and life time of OCs over 16 cycles at 650 °C were studied to investigate and optimize the structure of OC and process temperature with maximizing average methane conversion and hydrogen production yield. The synthesized OCs were characterized by multiples techniques. The results of X-ray powder diffraction (XRD and energy dispersive X-ray spectroscopy (EDX of reacted OCs showed that the presence of Y particles on the surface of OCs reduces the coke formation. The smaller NiO species were found for the yttrium promoted OC and therefore the distribution of Ni particles was improved. The reduction-oxidation (redox results revealed that 25Ni-2.5Y/SBA-16 OC has the highest catalytic activity of about 99.83% average CH4 conversion and 85.34% H2 production yield at reduction temperature of 650 °C with the steam to carbon molar ratio of 2.

Applications of solar reforming technology

Energy Technology Data Exchange (ETDEWEB)

Spiewak, I. [Weizmann Inst. of Science, Rehovoth (Israel); Tyner, C.E. [Sandia National Labs., Albuquerque, NM (United States); Langnickel, U. [Deutsche Forschungsanstalt fuer Luft- und Raumfahrt e.V. (DLR), Koeln (Germany)

1993-11-01

Research in recent years has demonstrated the efficient use of solar thermal energy for driving endothermic chemical reforming reactions in which hydrocarbons are reacted to form synthesis gas (syngas). Closed-loop reforming/methanation systems can be used for storage and transport of process heat and for short-term storage for peaking power generation. Open-loop systems can be used for direct fuel production; for production of syngas feedstock for further processing to specialty chemicals and plastics and bulk ammonia, hydrogen, and liquid fuels; and directly for industrial processes such as iron ore reduction. In addition, reforming of organic chemical wastes and hazardous materials can be accomplished using the high-efficiency destruction capabilities of steam reforming. To help identify the most promising areas for future development of this technology, we discuss in this paper the economics and market potential of these applications.

Evaluation of nickel and copper catalysts in biogas reforming for hydrogen production in SOFC

Energy Technology Data Exchange (ETDEWEB)

Silva, Leonardo Alves; Martins, Andre Rosa; Rangel, Maria do Carmo, E-mail: mcarmov@ufba.br [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Grupo de Estudos em Cinetica e Catalise; Ballarini, Adriana; Maina, Silvia [Instituto de Investigaciones en Catalisis Y Petroquimica Ing. Jose Miguel Parera (INCAPE), Santa Fe (Argentina)

2017-01-15

The solid oxide fuel cells (SOFC) enable the efficient generation of clean energy, fitting the current requirements of the growing demand for electricity and for the environment preservation. When powered with biogas (from digesters of municipal wastes), the SOFCs also contribute to reduce the environmental impact of these wastes. The most suitable route to produce hydrogen inside SOFC from biogas is through dry reforming but the catalyst is easily deactivated by coke, because of the high amounts of carbon in the stream. A promising way to overcome this drawback is by adding a second metal to nickel-based catalysts. Aiming to obtain active, selective and stable catalysts for biogas dry reforming, solids based on nickel (15%) and copper (5%) supported on aluminum and magnesium oxide were studied in this work. Samples were prepared by impregnating the support with nickel and copper nitrate, followed by calcination at 500, 600 and 800 deg C. It was noted that all solids were made of nickel oxide, nickel aluminate and magnesium aluminate but no copper compound was found. The specific surface areas did not changed with calcination temperature but the nickel oxide average particles size increased. The solids reducibility decreased with increasing temperature. All catalysts were active in methane dry reforming, leading to similar conversions but different selectivities to hydrogen and different activities in water gas shift reaction (WGSR). This behavior was assigned to different interactions between nickel and copper, at different calcination temperatures. All catalysts were active in WGSR, decreasing the hydrogen to carbon monoxide molar ratio and producing water. The catalyst calcined at 500 deg C was the most promising one, leading to the highest hydrogen yield, besides the advantage of being produced at the lowest calcination temperature, requiring less energy in its preparation. (author)

Evaluation of nickel and copper catalysts in biogas reforming for hydrogen production in SOFC

International Nuclear Information System (INIS)

Silva, Leonardo Alves; Martins, Andre Rosa; Rangel, Maria do Carmo

2017-01-01

The solid oxide fuel cells (SOFC) enable the efficient generation of clean energy, fitting the current requirements of the growing demand for electricity and for the environment preservation. When powered with biogas (from digesters of municipal wastes), the SOFCs also contribute to reduce the environmental impact of these wastes. The most suitable route to produce hydrogen inside SOFC from biogas is through dry reforming but the catalyst is easily deactivated by coke, because of the high amounts of carbon in the stream. A promising way to overcome this drawback is by adding a second metal to nickel-based catalysts. Aiming to obtain active, selective and stable catalysts for biogas dry reforming, solids based on nickel (15%) and copper (5%) supported on aluminum and magnesium oxide were studied in this work. Samples were prepared by impregnating the support with nickel and copper nitrate, followed by calcination at 500, 600 and 800 deg C. It was noted that all solids were made of nickel oxide, nickel aluminate and magnesium aluminate but no copper compound was found. The specific surface areas did not changed with calcination temperature but the nickel oxide average particles size increased. The solids reducibility decreased with increasing temperature. All catalysts were active in methane dry reforming, leading to similar conversions but different selectivities to hydrogen and different activities in water gas shift reaction (WGSR). This behavior was assigned to different interactions between nickel and copper, at different calcination temperatures. All catalysts were active in WGSR, decreasing the hydrogen to carbon monoxide molar ratio and producing water. The catalyst calcined at 500 deg C was the most promising one, leading to the highest hydrogen yield, besides the advantage of being produced at the lowest calcination temperature, requiring less energy in its preparation. (author)

A novel approach to the experimental study on methane/steam reforming kinetics using the Orthogonal Least Squares method

Science.gov (United States)

Sciazko, Anna; Komatsu, Yosuke; Brus, Grzegorz; Kimijima, Shinji; Szmyd, Janusz S.

2014-09-01

For a mathematical model based on the result of physical measurements, it becomes possible to determine their influence on the final solution and its accuracy. However, in classical approaches, the influence of different model simplifications on the reliability of the obtained results are usually not comprehensively discussed. This paper presents a novel approach to the study of methane/steam reforming kinetics based on an advanced methodology called the Orthogonal Least Squares method. The kinetics of the reforming process published earlier are divergent among themselves. To obtain the most probable values of kinetic parameters and enable direct and objective model verification, an appropriate calculation procedure needs to be proposed. The applied Generalized Least Squares (GLS) method includes all the experimental results into the mathematical model which becomes internally contradicted, as the number of equations is greater than number of unknown variables. The GLS method is adopted to select the most probable values of results and simultaneously determine the uncertainty coupled with all the variables in the system. In this paper, the evaluation of the reaction rate after the pre-determination of the reaction rate, which was made by preliminary calculation based on the obtained experimental results over a Nickel/Yttria-stabilized Zirconia catalyst, was performed.

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...

Use of catalytic reforming to aid natural gas HCCI combustion in engines: experimental and modelling results of open-loop fuel reforming

Energy Technology Data Exchange (ETDEWEB)

Peucheret, S.; Wyszynski, M.L.; Lehrle, R.S. [Future Power Systems Group, Mechanical Engineering, The University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Golunski, S. [Johnson Matthey, Technology Centre, Blount' s Court, Sonning Common, Reading RG4 9NH (United Kingdom); Xu, H. [Jaguar Land Rover Research, Jaguar Land Rover W/2/021, Abbey Road, Coventry CV3 4LF (United Kingdom)

2005-12-01

The potential of the homogeneous charge compression ignition (HCCI) combustion process to deliver drastically reduced emissions of NO{sub x} and improved fuel economy from internal combustion engines is well known. The process is, however, difficult to initiate and control, especially when methane or natural gas are used as fuel. To aid the HCCI combustion of natural gas, hydrogen addition has been successfully used in this study. This hydrogen can be obtained from on-line reforming of natural gas. Methane reforming is achieved here by reaction with engine exhaust gas and air in a small scale monolith catalytic reactor. The benchmark quantity of H{sub 2} required to enhance the feasibility and engine load range of HCCI combustion is 10%. For low temperature engine exhaust gas, typical for HCCI engine operating conditions, experiments show that additional air is needed to produce this quantity. Experimental results from an open-loop fuel exhaust gas reforming system are compared with two different models of basic thermodynamic equilibria calculations. At the low reactor inlet temperatures needed for the HCCI application (approx. 400 deg C) the simplified three-reaction thermodynamic equilibrium model is in broad agreement with experimental results, while for medium (550-650 deg C) inlet temperature reforming with extra air added, the high hydrogen yields predicted from the multi-component equilibrium model are difficult to achieve in a practical reformer. (author)

Reforming performance of a plasma-catalyst hybrid converter using low carbon fuels

International Nuclear Information System (INIS)

Horng, R.-F.; Lai, M.-P.; Huang, H.-H.; Chang, Y.-P.

2009-01-01

The reforming performance of a plasma-catalyst hybrid converter using different low carbon fuels was investigated. The methodology was to use arc from spark discharge combined with an appropriate oxygen/carbon molar ratio (O 2 /C) and feeding rate of the supplied mixture. To enhance the mixing and reforming reaction, a gas intake swirl was generated by inducing the mixture tangentially into the reaction chamber. The required energy for fuel processing was provided by heat released through the oxidation of the air-fuel mixture. The reforming temperature as well as the effect of steam addition on the hydrogen production was studied. The results showed that reformate gas temperature had a profound effect on the overall reaction. The H 2 /(CO + CO 2 ) ratio reformed by both methane and propane was shown to increase with temperature and that the optimum ratio was obtained when reforming methane under 650 deg. C. The conversion efficiency of the fuel was also shown to increase with increasing temperature. The best thermal efficiency of 72.01% was obtained near 750 deg. C. The theoretical equilibrium calculations and the experimental results were compared.

Anaerobic digestion for methane generation and ammonia reforming for hydrogen production: A thermodynamic energy balance of a model system to demonstrate net energy feasibility

International Nuclear Information System (INIS)

Babson, David M.; Bellman, Karen; Prakash, Shaurya; Fennell, Donna E.

2013-01-01

During anaerobic digestion, organic matter is converted to carbon dioxide and methane, and organic nitrogen is converted to ammonia. Generally, ammonia is recycled as a fertilizer or removed via nitrification–denitrification in treatment systems; alternatively it could be recovered and catalytically converted to hydrogen, thus supplying additional fuel. To provide a basis for further investigation, a theoretical energy balance for a model system that incorporates anaerobic digestion, ammonia separation and recovery, and conversion of the ammonia to hydrogen is reported. The model Anaerobic Digestion-Bioammonia to Hydrogen (ADBH) system energy demands including heating, pumping, mixing, and ammonia reforming were subtracted from the total energy output from methane and hydrogen to create an overall energy balance. The energy balance was examined for the ADBH system operating with a fixed feedstock loading rate with C:N ratios (gC/gN) ranging from 136 to 3 which imposed corresponding total ammonia nitrogen (TAN) concentrations of 20–10,000 mg/L. Normalizing total energy potential to the methane potential alone indicated that at a C:N ratio of 17, the energy output was greater for the ADBH system than from anaerobic digestion generating only methane. Decreasing the C:N ratio increased the methane content of the biogas comprising primarily methane to >80% and increased the ammonia stripping energy demand. The system required 23–34% of the total energy generated as parasitic losses with no energy integration, but when internally produced heat and pressure differentials were recovered, parasitic losses were reduced to between 8 and 17%. -- Highlights: •Modeled an integrated Anaerobic Digestion-Bioammonia to Hydrogen (ADBH) system. •Demonstrated positive net energy produced over a range of conditions by ADBH. •Demonstrated significant advantages of dual fuel recovery for energy gain by >20%. •Suggested system design considerations for energy recovery with

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

Science.gov (United States)

Malerød-Fjeld, Harald; Clark, Daniel; Yuste-Tirados, Irene; Zanón, Raquel; Catalán-Martinez, David; Beeaff, Dustin; Morejudo, Selene H.; Vestre, Per K.; Norby, Truls; Haugsrud, Reidar; Serra, José M.; Kjølseth, Christian

2017-11-01

Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 °C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.

SOFC direct fuelling with high-methane gases: Optimal strategies for fuel dilution and upgrade to avoid quick degradation

International Nuclear Information System (INIS)

Baldinelli, A.; Barelli, L.; Bidini, G.; Di Michele, A.; Vivani, R.

2016-01-01

Highlights: • SOFCs are operated on natural gas and biogas direct feeding. • Methane partial oxidation and dry reforming are compared. • The optimal oxygen-to-carbon stoichiometry to avoid degradation is determined for both natural gas and biogas. • NiYSZ anodes degradation mechanisms are investigated though SEM-EDX and XRD. - Abstract: In the outlook of the transition to the carbon-free society, low-carbon gases, such as natural gas or biogas, are very promising. The first is commonly used for stationary applications based on Solid Oxide Fuel Cells (SOFCs) equipped with external reformers. Similar installations are required when the SOFC is run on biogas. Yet, high SOFC operative temperature enables internal decomposition of light hydrocarbons, therefore allowing the suppression of external reforming. Evidently, this brings about benefits in terms of system complexity and cost reduction. Nonetheless, unlike reformate fuels, direct exposure to large amount of methane favours SOFC anodes degradation. Implementing a systematic experimental approach, this paper aims at determining a simple operative strategy to carry out direct feeding without meeting with quick degradation issues, producing interesting outcomes with regards to the management of SOFC-based systems. Particularly, the regulation of the oxygen-to-carbon (O/C) relative fraction of the fuel through air addition to natural gas and partial CO_2 separation from biogas is helpful in the prevention of those mechanisms. In this study, NiYSZ anode SOFCs are exposed to air-diluted natural gas and upgraded biogas, featuring O/C between 0.2 and 1.2. Tracing these cases, at 800 °C and 500 mA/cm"2 constant load, cell performances are measured over a time interval of 100 h. Finally, post-mortem analysis is performed on the specimens to investigate material morphological changes after the exposure to high-methane fuels. Results showed that O/C = 0.8 (+63% air) is the best case to employ air-diluted natural gas

Towards H2-rich gas production from unmixed steam reforming of methane: Thermodynamic modeling

Science.gov (United States)

Lima da Silva, Aline; Müller, Iduvirges Lourdes

2011-10-01

In this work, the Gibbs energy minimization method is applied to investigate the unmixed steam reforming (USR) of methane to generate hydrogen for fuel cell application. The USR process is an advanced reforming technology that relies on the use of separate air and fuel/steam feeds to create a cyclic process. Under air flow (first half of the cycle), a bed of Ni-based material is oxidized, providing the heat necessary for the steam reforming that occurs subsequently during fuel/steam feed stage (second half of the cycle). In the presence of CaO sorbent, high purity hydrogen can be produced in a single reactor. In the first part of this work, it is demonstrated that thermodynamic predictions are consistent with experimental results from USR isothermal tests under fuel/steam feed. From this, it is also verified that the reacted NiO to CH4 (NiOreacted/CH4) molar ratio is a very important parameter that affects the product gas composition and decreases with time. At the end of fuel/steam flow, the reforming reaction is the most important chemical mechanism, with H2 production reaching ∼75 mol%. On the other hand, at the beginning of fuel/steam feed stage, NiO reduction reactions dominate the equilibrium system, resulting in high CO2 selectivity, negative steam conversion and low concentrations of H2. In the second part of this paper, the effect of NiOreacted/CH4 molar ratio on the product gas composition and enthalpy change during fuel flow is investigated at different temperatures for inlet H2O/CH4 molar ratios in the range of 1.2-4, considering the USR process operated with and without CaO sorbent. During fuel/steam feed stage, the energy demand increases as time passes, because endothermic reforming reaction becomes increasingly important as this stage nears its end. Thus, the duration of the second half of the cycle is limited by the conditions under which auto-thermal operation can be achieved. In absence of CaO, H2 at concentrations of approximately 73 mol% can

Evidence for nitrite-dependent anaerobic methane oxidation as a previously overlooked microbial methane sink in wetlands

Science.gov (United States)

Hu, Bao-lan; Shen, Li-dong; Lian, Xu; Zhu, Qun; Liu, Shuai; Huang, Qian; He, Zhan-fei; Geng, Sha; Cheng, Dong-qing; Lou, Li-ping; Xu, Xiang-yang; Zheng, Ping; He, Yun-feng

2014-01-01

The process of nitrite-dependent anaerobic methane oxidation (n-damo) was recently discovered and shown to be mediated by “Candidatus Methylomirabilis oxyfera” (M. oxyfera). Here, evidence for n-damo in three different freshwater wetlands located in southeastern China was obtained using stable isotope measurements, quantitative PCR assays, and 16S rRNA and particulate methane monooxygenase gene clone library analyses. Stable isotope experiments confirmed the occurrence of n-damo in the examined wetlands, and the potential n-damo rates ranged from 0.31 to 5.43 nmol CO2 per gram of dry soil per day at different depths of soil cores. A combined analysis of 16S rRNA and particulate methane monooxygenase genes demonstrated that M. oxyfera-like bacteria were mainly present in the deep soil with a maximum abundance of 3.2 × 107 gene copies per gram of dry soil. It is estimated that ∼0.51 g of CH4 m−2 per year could be linked to the n-damo process in the examined wetlands based on the measured potential n-damo rates. This study presents previously unidentified confirmation that the n-damo process is a previously overlooked microbial methane sink in wetlands, and n-damo has the potential to be a globally important methane sink due to increasing nitrogen pollution. PMID:24616523

Improvements of reforming performance of a nuclear heated steam reforming process

International Nuclear Information System (INIS)

Hada, Kazuhiko

1996-10-01

Performance of an energy production process by utilizing high temperature nuclear process heat was not competitive to that by utilizing non-nuclear process heat, especially fossil-fired process heat due to its less favorable chemical reaction conditions. Less favorable conditions are because a temperature of the nuclear generated heat is around 950degC and the heat transferring fluid is the helium gas pressurized at around 4 MPa. Improvements of reforming performance of nuclear heated steam reforming process were proposed in the present report. The steam reforming process, one of hydrogen production processes, has the possibility to be industrialized as a nuclear heated process as early as expected, and technical solutions to resolve issues for coupling an HTGR with the steam reforming system are applicable to other nuclear-heated hydrogen production systems. The improvements are as follows: As for the steam reformer, (1) increase in heat input to process gas by applying a bayonet type of reformer tubes and so on, (2) increase in reforming temperature by enhancing heat transfer rate by the use of combined promoters of orifice baffles, cylindrical thermal radiation pipes and other proposal, and (3) increase in conversion rate of methane to hydrogen by optimizing chemical compositions of feed process gas. Regarding system arrangement, a steam generator and superheater are set in the helium loop as downstream coolers of the steam reformer, so as to effectively utilize the residual nuclear heat for generating feed steam. The improvements are estimated to achieve the hydrogen production rate of approximately 3800 STP-m 3 /h for the heat source of 10 MW and therefore will provide the potential competitiveness to a fossil-fired steam reforming process. Those improvements also provide the compactness of reformer tubes, giving the applicability of seamless tubes. (J.P.N.)

Improving carbon tolerance of Ni-YSZ catalytic porous membrane by palladium addition for low temperature steam methane reforming

Science.gov (United States)

Lee, Sang Moon; Won, Jong Min; Kim, Geo Jong; Lee, Seung Hyun; Kim, Sung Su; Hong, Sung Chang

2017-10-01

Palladium was added on the Ni-YSZ catalytic porous membrane by wet impregnation and electroless plating methods. Its surface morphology characteristics and carbon deposition properties for the low temperature steam methane reforming were investigated. The addition of palladium could obviously be enhanced the catalytic activity as well as carbon tolerance of the Ni-YSZ porous membrane. The porous membranes were evaluated by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR), CH4 temperature-programmed reduction (CH4-TPR), and O2 temperature-programmed oxidation (O2-TPO). It was found that the Pd-Ni-YSZ catalytic porous membrane showed the superior stability as well as the deposition of carbon on the surface during carbon dissociation adsorption at 650 °C was also suppressed.

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.

methanization of organic matters. Guide for project developers

International Nuclear Information System (INIS)

2015-02-01

This document aims at informing potential project developers (farmers, local communities, industrials) all along the creation of a methanization unit. It precisely indicates administrative procedures required to complete a project. It first presents some generalities about methanization (matters and their performance, methanization cycle, biogas), describes methanization processes (dry and humid), and valorisation processes (co-generation, hot water production, gas injection into the public network), presents digestate characteristics, and discusses benefits and drawbacks of methanization. The different steps of a project management are then analysed. Additional procedures are indicated, and risks and traps of methanization projects are highlighted. The document comes along with a large number of appendices which can be documents released by professional or public bodies

Methane generated from graphite--tritium interaction

International Nuclear Information System (INIS)

Coffin, D.O.; Walthers, C.R.

1979-01-01

When hydrogen isotopes are separated by cryogenic distillation, as little as 1 ppM of methane will eventually plug the still as frost accumulates on the column packings. Elemental carbon exposed to tritium generates methane spontaneously, and yet some dry transfer pumps, otherwise compatible with tritium, convey the gas with graphite rotors. This study was to determine the methane production rate for graphite in tritium. A pump manufacturer supplied graphite samples that we exposed to tritium gas at 0.8 atm. After 137 days we measured a methane synthesis rate of 6 ng/h per cm 2 of graphite exposed. At this rate methane might grow to a concentration of 0.01 ppM when pure tritium is transferred once through a typical graphite--rotor transfer pump. Such a low methane level will not cause column blockage, even if the cryogenic still is operated continuously for many years

Thermoelectric characterization of an intermediate temperature solid oxide fuel cell system directly fed by dry biogas

International Nuclear Information System (INIS)

De Lorenzo, G.; Corigliano, O.; Lo Faro, M.; Frontera, P.; Antonucci, P.; Zignani, S.C.; Trocino, S.; Mirandola, F.A.; Aricò, A.S.; Fragiacomo, P.

2016-01-01

Highlights: • Numerical Model (NM) of SOFC Cogenerative System (SCS) fed by dry biogas is set up. • NM simulates new Ni-Fe/CGO protective layer for direct CH_4 consumption at the anode. • NM simulates the anode carbonation phenomenon and is experimentally validated. • The performance parameters trends of SCS fed by three types of dry biogas are shown. • SEM images after 40 h of operation show that there is no anode carbon deposition. - Abstract: A properly manufactured intermediate temperature Solid Oxide Fuel Cell (SOFC) can be directly fed by dry biogas, considering also the electrochemical partial and total oxidation reactions of methane in the biogas at the anode. In this way the methane in the biogas is electrochemically consumed directly at the fuel cell without the need to mix the biogas with any reforming gas (steam, oxygen or carbon dioxide). In this article, a numerical model of an SOFC system with Ni-Fe/CGO electrocatalyst anode protective layer directly fed by dry biogas, in cogenerative arrangement and with anode exhaust gas recirculation is formulated. The influences of biogas composition, of fuel cell operating current density and of percentage of recirculated anode exhaust gas on the SOFC system performances were evaluated by calculation code. An SOFC test bench was set up to validate the calculation code results experimentally. Furthermore, the numerical model also considers the anode carbonation and evaluates the amount of carbon that can be formed in the anode at chemical equilibrium and quasi-equilibrium conditions associated with the specific anode protective layer used.

Removal of methane from compressed natural gas fueled vehicle exhaust

International Nuclear Information System (INIS)

Subramanian, S.; Kudla, R.J.; Chattha, M.S.

1992-01-01

The objective of this paper is to investigate the modes of methane (CH 4 ) removal from simulated compressed natural gas (CNG) fueled vehicle exhaust under net oxidizing, net reducing, and stoichiometric conditions. Model reaction studies were conducted. The results suggest that the oxidation of methane with oxygen contributes to the removal of methane under net oxidizing conditions. In contrast, the oxidation of methane with oxygen as well as nitric oxide contributes to its removal under net reducing conditions. The steam reforming reaction does not significantly contribute to the removal of methane. The methane conversions under net reducing conditions are higher than those observed under net oxidizing conditions. The study shows that the presence of carbon monoxide in the feed gas leads to a gradual decrease in the methane conversion with increasing redox ratio, under net oxidizing conditions. a minimum in methane conversion is observed at a redox ratio of 0. 8. The higher activity for the methane-oxygen reaction resulting from a lowering in the overall oxidation state of palladium and the contribution of the methane-nitric oxide reaction toward the removal of CH 4 appear to account for the higher CH 4 conversions observed under net reducing conditions

Enhanced catalytic behavior of Ni alloys in steam methane reforming

Science.gov (United States)

Yoon, Yeongpil; Kim, Hanmi; Lee, Jaichan

2017-08-01

The dissociation process of methane on Ni and Ni alloys are investigated by density functional theory (DFT) in terms of catalytic efficiency and carbon deposition. Examining the dissociation to CH3, CH2, CH, C, and H is not sufficient to properly predict the catalytic efficiency and carbon deposition, and further investigation of the CO gas-evolving reaction is required to completely understand methane dissociation in steam. The location of alloying element in Ni alloy needed be addressed from the results of ab-inito molecular dynamics (MD). The reaction pathway of methane dissociation associated with CO gas evolution is traced by performing first-principles calculations of the adsorption and activation energies of each dissociation step. During the dissociation process, two alternative reaction steps producing adsorbed C and H or adsorbed CO are critically important in determining coking inhibition as well as H2 gas evolution (i.e., the catalytic efficiency). The theoretical calculations presented here suggest that alloying Ni with Ru is an effective way to reduce carbon deposition and enhance the catalytic efficiency of H2 fueling in solid oxide fuel cells (SOFCs).

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.

Journal of Chemical Sciences | Indian Academy of Sciences

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 ...

Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported Ni and Co Catalysts: Full Factorial Design Screening

Directory of Open Access Journals (Sweden)

M. Anwar Hossain

2018-01-01

Full Text Available In this study, the potential of dry reforming reaction over CaFe2O4 supported Ni and Co catalysts were investigated. The Co/CaFe2O4 and Ni/CaFe2O4 catalysts were synthesized using wet impregnation method by varying the metal loading from 5-15 %. The synthesized catalysts were tested in methane dry reforming reaction at atmospheric pressure and reaction temperature ranged 700-800 oC. The catalytic performance of the catalysts based on the initial screening is ranked as 5%Co/CaFe2O4 < 10%Co/CaFe2O4 < 5%Ni/CaFe2O4 < 10%Ni/CaFe2O4 according to their performance. The Ni/CaFe2O4 catalyst was selected for further investigation using full factorial design of experiment. The interaction effects of three factors namely metal loading (5-15 %, feed ratio (0.4-1.0, and reaction temperature (700-800 oC were evaluated on the catalytic activity in terms of CH4 and CO2 conversion as well as H2 and CO yield. The interaction between the factors showed significant effects on the catalyst performance at metal loading, feed ratio and reaction temperature of 15 %, 1.0, and 800 oC. respectively. The 15 wt% Ni/CaFe2O4 was subsequently characterized by Thermogravimetric (TGA, X-ray Diffraction (XRD, Field Emission Scanning Electron Microscopy (FESEM, Energy Dispersive X-ray Spectroscopy (EDX, X-ray Photoelectron Spectroscopy (XPS, N2-physisorption, Temperature Programmed Desorption (TPD-NH3, TPD-CO2, and Fourier Transform Infra Red (FTIR to ascertain its physiochemical properties.  This study demonstrated that the CaFe2O4 supported Ni catalyst has a good potential to be used for syngas production via methane dry reforming. Copyright © 2018 BCREC Group. All rights reserved Received: 5th May 2017; Revised: 8th August 2017; Accepted: 9th August 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Hossain, M.A., Ayodele, B.V., Cheng, C.K., Khan, M.R. (2018. Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported

Hydrogen production by catalytic processing of renewable methane-rich gases

Energy Technology Data Exchange (ETDEWEB)

Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, Cocoa, FL 32922-5703 (United States)

2008-04-15

Biomass-derived methane-rich gases such as landfill gas (LFG), biogas and digester gas are promising renewable resources for near-future production of hydrogen. The technical and economical feasibility of hydrogen production via catalytic reforming of LFG and other methane-rich gases is evaluated in this paper. The thermodynamic equilibrium calculations and experimental measurements of reformation of methane-rich CH{sub 4}-CO{sub 2} mixtures over Ni-based catalyst were conducted. The problems associated with the catalyst deactivation due to carbon lay down and effects of steam and oxygen on the process sustainability were explored. Two technological approaches distinguished by the mode of heat input to the endothermic process (i.e., external vs autothermal) were modeled using AspenPlus trademark chemical process simulator and validated experimentally. A 5 kW{sub th} pilot unit for hydrogen production from LFG-mimicking CH{sub 4}-CO{sub 2} mixture was fabricated and operated. A preliminary techno-economic assessment indicates that the liquid hydrogen production costs are in the range of 3.00-7.00 per kilogram depending upon the plant capacity, the process heat input option and whether or not carbon sequestration is included in the process. (author)

Hydrogen production by reforming of hydrocarbons and alcohols in a dielectric barrier discharge

Energy Technology Data Exchange (ETDEWEB)

Sarmiento, Belen; Brey, J. Javier; Viera, Inmaculada G. [Hynergreen Technologies, S.A. Avda. de la Buhaira, 2. 41018 Sevilla (Spain); Gonzalez-Elipe, Agustin R.; Cotrino, Jose; Rico, Victor J. [Instituto de Ciencia de los Materiales de Sevilla (CSIC-University Sevilla), Avda. Americo Vespucio, 49, 41092 Sevilla (Spain)

2007-06-10

This work reports about the use of plasmas to obtain hydrogen by reforming of hydrocarbons or alcohols in mixtures with CO{sub 2} or H{sub 2}O. The plasma is activated in a dielectric barrier discharge (DBD) reactor working at atmospheric pressure and low temperatures (i.e., about 100 C). The reactor presents a great versatility in operation and a low manufacturing cost. Results are presented for the reforming of methane, methanol and ethanol. Methane transforms up to a 70% into CO and H{sub 2} without formation of any kind of superior hydrocarbon. For the two alcohols 100% conversion into the same products is found for flows much higher than in the case of methane. The work reports a description of the reactor and the operational conditions of the power supply enabling the ignition of the plasma and its steady state operation. (author)

Optimizing a steam-methane reformer for hydrogen production

NARCIS (Netherlands)

de Jong, M.; Reinders, Angelina H.M.E.; Kok, Jacobus B.W.; Westendorp, G.

2009-01-01

By means of steam reforming, natural gas is converted to carbon dioxide and hydrogen. The reactions take place in reactor tubes which are covered with catalyst at the inside, where the reactive mixture flows. At the outside they are heated by combustion of natural gas with air. In this paper the

Catalytic steam methane reforming over Ir/Ce{sub 0.9}Gd{sub 0.1}O{sub 2-x}: resistance to coke formation and sulfur poisoning

Energy Technology Data Exchange (ETDEWEB)

Postole, G.; Girona, K.; Kaddouri, A.; Gelin, P. [Institut de Recherches sur la Catalyse et l' Environnement de Lyon, Universite Lyon 1, CNRS, UMR 5256, IRCELYON, F-69626 Villeurbanne Cedex (France); Toyir, J. [Institut de Recherches sur la Catalyse et l' Environnement de Lyon, Universite Lyon 1, CNRS, UMR 5256, IRCELYON, F-69626 Villeurbanne Cedex (France); Universite Sidi Mohamed Ben Abdellah Fes, FP-Taza, B.P. 1223 Taza (Morocco)

2012-04-15

This work investigates the catalytic properties of Ir/Ce{sub 0.9}Gd{sub 0.1}O{sub 2-x} (Ir/CGO) catalyst and CGO support in steam reforming of methane in the absence or presence of H{sub 2}S (50 ppm) for further application in a solid oxide fuel cell (SOFC) working under methane at intermediate temperatures and integrating a gradual internal reforming concept. The catalytic activity was measured at 750 C by using a 50 mol.% CH{sub 4}/5 mol.% H{sub 2}O/45 mol.% N{sub 2} mixture and a 10 mol.% CH{sub 4}/90 mol.% N{sub 2} mixture. The addition of Ir to CGO improves the catalytic activity in hydrogen production by two orders of magnitude with respect to that of CGO alone. Temperature programmed oxidation experiments were performed after reaction in both types of mixtures to study the eventual formation of carbon deposits. Over Ir/CGO, carbon formed in little amounts (even in the absence of H{sub 2}O in the feed), being highly reactive toward O{sub 2}. Upon H{sub 2}S addition, the CGO support exhibited surprisingly an improved catalytic activity on the contrary to Ir/CGO which partly deactivated. Upon suppression of H{sub 2}S in the feed the initial catalytic activity was fully restored for both catalysts. The catalytic behavior of CGO in the presence of H{sub 2}S was discussed, based upon temperature programmed reaction of CH{sub 4}. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Impact of cell design and operating conditions on the performances of SOFC fuelled with methane

Science.gov (United States)

Laurencin, J.; Lefebvre-Joud, F.; Delette, G.

An in-house-model has been developed to study the thermal and electrochemical behaviour of a planar SOFC fed directly with methane and incorporated in a boiler. The usual Ni-YSZ cermet has been considered for the anode material. It has been found that methane reforming into hydrogen occurs only at the cell inlet in a limited depth within the anode. A sensitivity analysis has allowed establishing that anode thicknesses higher than ∼400-500 μm are required to achieve both the optimal methane conversion and electrochemical performances. The direct internal reforming (DIR) mechanisms and the impact of operating conditions on temperature gradients and SOFC electrical efficiencies have been investigated considering the anode supported cell configuration. It has been shown that the temperature gradient is minimised in the autothermal mode of cell operation. Thermal equilibrium in the stack has been found to be strongly dependent on radiative heat losses with the stack envelope. Electrochemical performance and cell temperature maps have been established as a function of methane flow rates and cell voltages.

Methane steam reforming kinetics over Ni-YSZ anodematerials for Solid Oxide FuelCells

DEFF Research Database (Denmark)

Mogensen, David

of internal reforming has to be carefully controlled. The objective of this thesis is to make such a careful control possible by examining the rate of internal steam reforming in SOFCs. The catalytic steam reforming activity of Ni-YSZ anode material was tested both in a packed bed reactor to determine...

Preliminary risk analysis of an Hydrogen production plant using the reformed process of methane with vapor coupled to a high temperature nuclear reactor; Analisis preliminar de riesgo de una planta de produccion de hidrogeno utilizando el proceso de reformado de metano con vapor acoplada a un reactor nuclear de alta temperatura

Energy Technology Data Exchange (ETDEWEB)

Flores y Flores, A. [Facultad de Ingenieria, UNAM, 04510 Mexico D.F. (Mexico)]. E-mail: alain_fyf@yahoo.com; Nelson E, P.F.; Francois L, J.L. [Facultad de Ingenieria, Laboratorio de Analisis en Ingenieria de Reactores Nucleares, UNAM, Paseo Cuauhnahuac 8532, 62550 Jiutepec, Morelos (Mexico)

2004-07-01

It is necessary to identify the different types of dangers, as well as their causes, probabilities and consequences of the same ones, inside plants, industries and any process to classify the risks. This work is focused in particular to a study using the technical HAZOP (Hazard and Operability) for a plant of reformed of methane with vapor coupled to a nuclear reactor of the type HTTR (High Temperature Test Reactor), which is designed to be built in Japan. In particular in this study the interaction is analyzed between the nuclear reactor and the plant of reformed of methane with vapor. After knowing the possible causes of risk one it is built chart of results of HAZOP to have a better vision of the consequences of this faults toward the buildings and constructions, to people and the influence of the fault on each plant; for what there are proposed solutions to mitigate these consequences or to avoid them. The work is divided in three sections: a brief introduction about the technique of HAZOP; some important aspects of the plant of reformed of methane with vapor; and the construction of the chart of results of HAZOP. (Author)

Chemical looping reforming in packed-bed reactors : modelling, experimental validation and large-scale reactor design

NARCIS (Netherlands)

Spallina, V.; Marinello, B.; Gallucci, F.; Romano, M.C.; van Sint Annaland, M.

This paper addresses the experimental demonstration and model validation of chemical looping reforming in dynamically operated packed-bed reactors for the production of H2 or CH3OH with integrated CO2 capture. This process is a combination of auto-thermal and steam methane reforming and is carried

Understanding the physiological and molecular mechanisms of rice-microbial interactions that produce methane

Science.gov (United States)

The second most abundant greenhouse gas, methane, is ~25 times more potent in global warming potential than carbon dioxide, and 7-17% of atmospheric methane comes from flooded rice fields. Methane emissions can be greatly reduced by using alternate wetting and drying irrigation management and/or cul...

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)

Catalytic aromatization of methane.

Science.gov (United States)

Spivey, James J; Hutchings, Graham

2014-02-07

Recent developments in natural gas production technology have led to lower prices for methane and renewed interest in converting methane to higher value products. Processes such as those based on syngas from methane reforming are being investigated. Another option is methane aromatization, which produces benzene and hydrogen: 6CH4(g) → C6H6(g) + 9H2(g) ΔG°(r) = +433 kJ mol(-1) ΔH°(r) = +531 kJ mol(-1). Thermodynamic calculations for this reaction show that benzene formation is insignificant below ∼600 °C, and that the formation of solid carbon [C(s)] is thermodynamically favored at temperatures above ∼300 °C. Benzene formation is insignificant at all temperatures up to 1000 °C when C(s) is included in the calculation of equilibrium composition. Interestingly, the thermodynamic limitation on benzene formation can be minimized by the addition of alkanes/alkenes to the methane feed. By far the most widely studied catalysts for this reaction are Mo/HZSM-5 and Mo/MCM-22. Benzene selectivities are generally between 60 and 80% at methane conversions of ∼10%, corresponding to net benzene yields of less than 10%. Major byproducts include lower molecular weight hydrocarbons and higher molecular weight substituted aromatics. However, carbon formation is inevitable, but the experimental findings show this can be kinetically limited by the use of H2 or oxidants in the feed, including CO2 or steam. A number of reactor configurations involving regeneration of the carbon-containing catalyst have been developed with the goal of minimizing the cost of regeneration of the catalyst once deactivated by carbon deposition. In this tutorial review we discuss the thermodynamics of this process, the catalysts used and the potential reactor configurations that can be applied.

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).

Catalytic conversion of methane: Carbon dioxide reforming and oxidative coupling

KAUST Repository

Takanabe, Kazuhiro

2012-01-01

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

Microstructural study of Ni/γ-Al2O3 catalyst: addition effects of CeO2 on carbon dioxide reforming of methane

International Nuclear Information System (INIS)

Valentini, Antoninho; Probst, Luiz Fernando Dias; Carreno, Neftali L. V.; Leite, Edson R.; Pontes, Fenelon M.; Longo, Elson; Schreiner, Wido H.; Lisboa-Filho, Paulo N.

2003-01-01

The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the γ-Al 2 O 3 /CeO 2 system prepared by wet impregnation. With the increase of the Co2 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, H 2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO 2 was observed to the Ni/CeO 2 sample after activation in a H 2 atmosphere above 300 deg C. Such behavior has a significantly influence on the catalytic activity. (author)

Bio-oil steam reforming, partial oxidation or oxidative steam reforming coupled with bio-oil dry reforming to eliminate CO{sub 2} emission

Energy Technology Data Exchange (ETDEWEB)

Hu, Xun [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Lu, Gongxuan [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

2010-07-15

Biomass is carbon-neutral and utilization of biomass as hydrogen resource shows no impact on atmospheric CO{sub 2} level. Nevertheless, a significant amount of CO{sub 2} is always produced in biomass gasification processes. If the CO{sub 2} produced can further react with biomass, then the biomass gasification coupled with CO{sub 2} reforming of biomass will result in a net decrease of CO{sub 2} level in atmosphere and produce the chemical raw material, syngas. To achieve this concept, a ''Y'' type reactor is developed and applied in bio-oil steam reforming, partial oxidation, or oxidative steam reforming coupled with CO{sub 2} reforming of bio-oil to eliminate the emission of CO{sub 2}. The experimental results show that the reaction systems can efficiently suppress the emission of CO{sub 2} from various reforming processes. The different coupled reaction systems generate the syngas with different molar ratio of CO/H{sub 2}. In addition, coke deposition is encountered in the different reforming processes. Both catalysts and experimental parameters significantly affect the coke deposition. Ni/La{sub 2}O{sub 3} catalyst shows much higher resistivity toward coke deposition than Ni/Al{sub 2}O{sub 3} catalyst, while employing high reaction temperature is vital for elimination of coke deposition. Although the different coupled reaction systems show different characteristic in terms of product distribution and coke deposition, which all can serve as methods for storage of the carbon from fossil fuels or air. (author)

Preparation of Palladium-Impregnated Ceria by Metal Complex Decomposition for Methane Steam Reforming Catalysis

Directory of Open Access Journals (Sweden)

Worawat Wattanathana

2017-01-01

Full Text Available Palladium-impregnated ceria materials were successfully prepared via an integrated procedure between a metal complex decomposition method and a microwave-assisted wetness impregnation. Firstly, ceria (CeO2 powders were synthesized by thermal decomposition of cerium(III complexes prepared by using cerium(III nitrate or cerium(III chloride as a metal source to form a metal complex precursor with triethanolamine or benzoxazine dimer as an organic ligand. Palladium(II nitrate was consequently introduced to the preformed ceria materials using wetness impregnation while applying microwave irradiation to assist dispersion of the dopant. The palladium-impregnated ceria materials were obtained by calcination under reduced atmosphere of 10% H2 in He stream at 700°C for 2 h. Characterization of the palladium-impregnated ceria materials reveals the influences of the metal complex precursors on the properties of the obtained materials. Interestingly, the palladium-impregnated ceria prepared from the cerium(III-benzoxazine dimer complex revealed significantly higher BET specific surface area and higher content of the more active Pdδ+ (δ > 2 species than the materials prepared from cerium(III-triethanolamine complexes. Consequently, it exhibited the most efficient catalytic activity in the methane steam reforming reaction. By optimization of the metal complex precursors, characteristics of the obtained palladium-impregnated ceria catalysts can be modified and hence influence the catalytic activity.

Dynamic simulation of a furnace of steam reforming of natural gas

International Nuclear Information System (INIS)

Acuna, A; Fuentes, C; Smith, C A

1999-01-01

Steam reforming of natural gas is a very important industrial process in refineries and ammonia and methanol plants. Hydrogen is produced by reforming methane with steam. This hydrogen is essential in the hydro-treating process in the refineries thus, it is important to supervise and control the performance of the hydrogen plant. Mathematical models of refineries and chemical plants are used to simulate the behavior of the process units. However, the models especially of reactors like reformers are not very reliable. This paper presents a dynamic model of a furnace-reactor. The simulation results are validated with industrial data

Staged catalytic gasification/steam reforming of pyrolysis oil

NARCIS (Netherlands)

van Rossum, G.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

2009-01-01

Gasification/steam reforming of pyrolysis oil was studied in a staged reactor concept, which consisted of an inert fluidized bed and a catalytic fixed bed. Methane and C2−C3 free syngas is produced at a single temperature around 800 °C at atmospheric pressure. By lowering the temperature of the

Hydrogen Production From catalytic reforming of greenhouse gases ...

African Journals Online (AJOL)

ADOWIE PERE

a fixed bed stainless steel reactor. The 20wt%. ... catalytic activity for hydrogen production with the highest yield and selectivity of 32.5% and 17.6% respectively. © JASEM ... CO2 reforming of methane is however not fully developed ..... Design and preparation of .... catalytic nickel membrane for gas to liquid (GTL) process.

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.

Experimental follow-up of the Bois-Joly GAEC methanization installation - Global assessment, final report, Phase 2 - Unit follow-up protocol. Operation assessment of the Bois-Joly GAEC agricultural discontinuous dry methanization unit. The discontinuous dry process: lessons learned after 6 years of exploitation at the Bois-Joly GAEC

International Nuclear Information System (INIS)

Brosset, Denis; Pouech, Philippe; Guillet, Marie; Banville, Sandrine; Bastide, Guillaume; Thual, J.

2008-06-01

A first document reports the follow-up study of an existing methanization installation. This study comprises four phases. The first one is a general presentation of the installation. The second one addresses the determination of reference indicators and the definition of the follow-up protocol. The third one is an installation follow-up over two years. The report thus proposes a presentation of the exploitation principles and operation, technical data regarding the methanization installation, the definition of follow-up parameters, protocol and means. It reports the elaboration of technical, environmental and economic indicators, and proposes an analysis of the installation performance, assets and weaknesses while outlining interests and perspectives of a formatted follow-up of methanization installations. Appendices notably contain the phase 2 report related to the unit follow-up protocol, results of physical-chemical composition analyses and of performance tests, a synthetic report of the experimental follow-up. A Power Point presentation reports the operation assessment. Another one proposes a discussion of lessons learned after 6 years of operation of the studied installation and more particularly about its discontinuous dry process. Another Power Point comments the relationship between research and application in the case of this specific process. Two documents and leaflets present the installation and a synthetic report of its experimental follow-up

Methane steam reforming kinetics over Ni-YSZ anode materials for Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Mogensen, David

of internal reforming has to be carefully controlled. The objective of this thesis is to make such a careful control possible by examining the rate of internal steam reforming in SOFCs. The catalytic steam reforming activity of Ni-YSZ anode material was tested both in a packed bed reactor to determine...

Methane fluxes from the mound-building termite species of North Australian savannas

Science.gov (United States)

Jamali, H.; Livesely, S. J.; Arndt, S. K.; Dawes-Gromadzki, T.; Cook, G. D.; Hutley, L.

2009-04-01

Termites are estimated to contribute 3-19% to the global methane emissions. These estimates have large uncertainties because of the limited number of field-based studies and species studied, as well as issues of diel and seasonal variation. We measured methane fluxes from four common mound-building termite species (Microcerotermes nervosus, n=26; M. serratus, n=4; Tumulitermes pastinator, n=5; and Amitermes darwini, n=4) in tropical savannas near Darwin in the Northern Territory, Australia. Methane fluxes from replicated termite mounds were measured in the field using manual chambers with fluxes reported on a mound volume basis. Methane flux was measured in both wet and dry seasons and diel variation was investigated by measuring methane flux every 4 hours over a 24 hour period. Mound temperature was measured concurrently with flux to examine this relationship. In addition, five M. nervosus mounds removed from the field and incubated under controlled temperature conditions over a 24 hour period to remove the effect of varying temperature. During the observation campaigns, mean monthly minimum and maximum temperatures for February (wet season) were 24.7 and 30.8°C, respectively, and were 20.1 to 31.4 °C in June (dry season). Annual rainfall in 2008 for Darwin was 1970.1 mm, with a maximum of 670 mm falling in February and no rain in May and June. Methane fluxes were greatest in the wet season for all species, ranging from 265.1±101.1 (T. pastinator) to 2256.6±757.1 (M. serratus) µg CH4-C/m3/h. In the dry season, methane fluxes were at their lowest, ranging from 10.0±5.5 (T. pastinator) to 338.0±165.9 (M. serratus) µg CH4-C/m3/h. On a diel basis, methane fluxes were smallest at the coolest time of the day (~0700 hrs) and greatest at the warmest (~1400 hrs) for all species, and for both wet and dry seasons. Typical diel variation in flux from M. serratus dominated mounds ranged from 902.6±261.9 to 1392.1±408.1 µg CH4-C/m3/h in wet season and 99.6±57.4 to

Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

International Nuclear Information System (INIS)

Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

2016-01-01

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 4 ) and carbon dioxide (CO 2 ) into syngas (mixture of CO and H 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.

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.

Steam reforming of commercial ultra-low sulphur diesel

Energy Technology Data Exchange (ETDEWEB)

Boon, J.; Van Dijk, E.; De Munck, S.; Van den Brink, R. [Energy research Centre of The Netherlands, ECN Hydrogen and Clean Fossil Fuels, P.O. Box 1, NL1755ZG Petten (Netherlands)

2011-03-11

Two main routes for small-scale diesel steam reforming exist: low-temperature pre-reforming followed by well-established methane steam reforming on the one hand and direct steam reforming on the other hand. Tests with commercial catalysts and commercially obtained diesel fuels are presented for both processes. The fuels contained up to 6.5 ppmw sulphur and up to 4.5 vol.% of biomass-derived fatty acid methyl ester (FAME). Pre-reforming sulphur-free diesel at around 475C has been tested with a commercial nickel catalyst for 118 h without observing catalyst deactivation, at steam-to-carbon ratios as low as 2.6. Direct steam reforming at temperatures up to 800C has been tested with a commercial precious metal catalyst for a total of 1190 h with two catalyst batches at steam-to-carbon ratios as low as 2.5. Deactivation was neither observed with lower steam-to-carbon ratios nor for increasing sulphur concentration. The importance of good fuel evaporation and mixing for correct testing of catalysts is illustrated. Diesel containing biodiesel components resulted in poor spray quality, hence poor mixing and evaporation upstream, eventually causing decreasing catalyst performance. The feasibility of direct high temperature steam reforming of commercial low-sulphur diesel has been demonstrated.

Steam reforming of commercial ultra-low sulphur diesel

Science.gov (United States)

Boon, Jurriaan; van Dijk, Eric; de Munck, Sander; van den Brink, Ruud

Two main routes for small-scale diesel steam reforming exist: low-temperature pre-reforming followed by well-established methane steam reforming on the one hand and direct steam reforming on the other hand. Tests with commercial catalysts and commercially obtained diesel fuels are presented for both processes. The fuels contained up to 6.5 ppmw sulphur and up to 4.5 vol.% of biomass-derived fatty acid methyl ester (FAME). Pre-reforming sulphur-free diesel at around 475 °C has been tested with a commercial nickel catalyst for 118 h without observing catalyst deactivation, at steam-to-carbon ratios as low as 2.6. Direct steam reforming at temperatures up to 800 °C has been tested with a commercial precious metal catalyst for a total of 1190 h with two catalyst batches at steam-to-carbon ratios as low as 2.5. Deactivation was neither observed with lower steam-to-carbon ratios nor for increasing sulphur concentration. The importance of good fuel evaporation and mixing for correct testing of catalysts is illustrated. Diesel containing biodiesel components resulted in poor spray quality, hence poor mixing and evaporation upstream, eventually causing decreasing catalyst performance. The feasibility of direct high temperature steam reforming of commercial low-sulphur diesel has been demonstrated.

In-Space Propulsion, Logistics Reduction, and Evaluation of Steam Reformer Kinetics: Problems and Prospects

Science.gov (United States)

Jaworske, D. A.; Palaszewski, B. A.; Kulis, M. J.; Gokoglu, S. A.

2015-01-01

Human space missions generate waste materials. A 70-kg crewmember creates a waste stream of 1 kg per day, and a four-person crew on a deep space habitat for a 400+ day mission would create over 1600 kg of waste. Converted into methane, the carbon could be used as a fuel for propulsion or power. The NASA Advanced Exploration Systems (AES) Logistics Reduction and Repurposing (LRR) project is investing in space resource utilization with an emphasis on repurposing logistics materials for useful purposes and has selected steam reforming among many different competitive processes as the preferred method for repurposing organic waste into methane. Already demonstrated at the relevant processing rate of 5.4 kg of waste per day, high temperature oxygenated steam consumes waste and produces carbon dioxide, carbon monoxide, and hydrogen which can then be converted into methane catalytically. However, the steam reforming process has not been studied in microgravity. Data are critically needed to understand the mechanisms that allow use of steam reforming in a reduced gravity environment. This paper reviews the relevant literature, identifies gravity-dependent mechanisms within the steam gasification process, and describes an innovative experiment to acquire the crucial kinetic information in a small-scale reactor specifically designed to operate within the requirements of a reduced gravity aircraft flight. The experiment will determine if the steam reformer process is mass-transport limited, and if so, what level of forced convection will be needed to obtain performance comparable to that in 1-g.

Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

Science.gov (United States)

Beck, Rainer

2004-03-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.

A numerical analysis of heat and mass transfer during the steam reforming process of ethane

Science.gov (United States)

Tomiczek, Marcin; Kaczmarczyk, Robert; Mozdzierz, Marcin; Brus, Grzegorz

2017-11-01

This paper presents a numerical analysis of heat and mass transfer during the steam reforming of ethane. From a chemical point of view, the reforming process of heavy hydrocarbons, such as ethane, is complex. One of the main issue is a set of undesired chemical reactions that causes the deposition of solid carbon and consequently blocks the catalytic property of a reactor. In the literature a carbon deposition regime is selected by thermodynamical analysis to design safe operation conditions. In the case of Computational Fluid Dynamic (CFD, hereafter) models each control volume should be investigated to determinate if carbon deposition is thermodynamically favourable. In this paper the authors combine equilibrium and kinetics analysis to simulate the steam reforming of methane-ethane rich fuel. The results of the computations were juxtaposed with experimental data for methane steam reforming, and good agreement was found. An analysis based on the kinetics of reactions was conducted to predict the influence of temperature drop and non-equilibrium composition on solid carbon deposition. It was found that strong non-uniform temperature distribution in the reactor causes conditions favourable for carbon deposition at the inlet of the reformer. It was shown that equilibrium calculations, often used in the literature, are insufficient.

CO2 reforming of methane: valorizing CO2 by means of Dielectric Barrier Discharge

Science.gov (United States)

Machrafi, H.; Cavadias, S.; Amouroux, J.

2011-03-01

The impact of pollution on the environment is causing several problems that are to be reduced as much as possible. One important example is the production of CO2 that is emitted by many transport and industrial applications. An interesting solution is to view CO2 as a source instead of a product that can be stocked. The case considered in this work is the CO2 reformation of methane producing hydrogen and CO. It is an endothermic reaction, for which the activition barrier needs to be overcome. The method of Dielectric Barrier Discharge can do this efficiently. The process relies on the collision of electrons, which are accelerated under an electrical field that is created in the discharge area. This leads to the formation of reactive species, which facilitate the abovementioned reaction. The determination of the electron density is performed by PLASIMO. The study is subsequently continued using the Reaction Engineering module in COMSOL (with an incorporated kinetic mechanism) in order to model the discharge phase. Then COMSOL (continuity and Navier-Stokes equations) is used to model the flow in the post-discharge phase. The results showed that both a 2D and 3D model can be used to model the chemical-plasma process. These methods need strongly reduced kinetic mechanism, which in some cases can cause loss of precision. It is also observed that the present experimental set-up that is modeled needs to be improved. A suggestion is made.

Estimation of transient heat flux density during the heat supply of a catalytic wall steam methane reformer

Science.gov (United States)

Settar, Abdelhakim; Abboudi, Saïd; Madani, Brahim; Nebbali, Rachid

2018-02-01

Due to the endothermic nature of the steam methane reforming reaction, the process is often limited by the heat transfer behavior in the reactors. Poor thermal behavior sometimes leads to slow reaction kinetics, which is characterized by the presence of cold spots in the catalytic zones. Within this framework, the present work consists on a numerical investigation, in conjunction with an experimental one, on the one-dimensional heat transfer phenomenon during the heat supply of a catalytic-wall reactor, which is designed for hydrogen production. The studied reactor is inserted in an electric furnace where the heat requirement of the endothermic reaction is supplied by electric heating system. During the heat supply, an unknown heat flux density, received by the reactive flow, is estimated using inverse methods. In the basis of the catalytic-wall reactor model, an experimental setup is engineered in situ to measure the temperature distribution. Then after, the measurements are injected in the numerical heat flux estimation procedure, which is based on the Function Specification Method (FSM). The measured and estimated temperatures are confronted and the heat flux density which crosses the reactor wall is determined.

Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

Science.gov (United States)

Khan, M. N.; Shamim, T.

2017-08-01

Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

Methane emissions from termites - landscape level estimates and methods of measurement

Science.gov (United States)

Jamali, Hizbullah; Livesley, Stephen J.; Hutley, Lindsay B.; Arndt, Stefan K.

2013-04-01

Termites contribute between mound-building termite species diurnally and seasonally in tropical savannas in the Northern Territory, Australia. Our results showed that there were significant diel and seasonal variations of methane emissions from termite mounds and we observed large species-specific differences. On a diurnal basis, methane fluxes were least at the coolest time of the day and greatest at the warmest for all species for both wet and dry seasons. We observed a strong and significant positive correlation between methane flux and mound temperature for all species. Fluxes in the wet season were 5-26-fold greater than those in the dry season and this was related to population dynamics of the termites. We observed significant relationships between mound methane flux and mound carbon dioxide flux, enabling the prediction of methane flux from measured carbon dioxide flux. However, these relationships were clearly termite species specific. We also determined significant relationships between mound flux and gas concentration inside mound, for both gases, and for all termite species, thereby enabling the prediction of flux from measured mound internal gas concentration. However, these relationships were also termite species specific. Consequently, there was no generic relationship that would enable an easier prediction of methane flux from termite mounds. On a landscape scale we estimated that termites were a methane source of +0.24 kg methane-C ha-1 year-1 whilst savanna soils were a methane sink of 1.14 kg methane-C ha-1 year-1. Termites therefore only offset 21% of methane consumed by savanna soil resulting in net sink strength of -0.90 kg methane-C ha-1 year-1 for these savannas. Assuming a similar contribution of termites in the savannas and tropical rain forests worldwide, termites would globally produce around 27 Tg CO2-e year-1, which is 0.2% of the global methane source budget or an order of magnitude smaller than many of the previous estimates.

Methane as a climate gas

Energy Technology Data Exchange (ETDEWEB)

Karlsdottir, S.

1996-03-01

This paper was read at the workshop ``The Norwegian Climate and Ozone Research Programme`` held on 11-12 March 1996. Methane is a key component in the atmosphere where its concentration has increased rapidly since pre-industrial time. About 2/3 of it is caused by human activities. Changes in methane will affect the concentrations of other gases, and a model is a very important tool to study sensitivity due to changes in concentration of gases. The author used a three-dimensional global chemistry transport model to study the effect of changes in methane concentration on other trace gases. The model includes natural and anthropogenic emissions of NOx, CO, CH{sub 4} and non-methane hydrocarbons. Wet and dry deposition are also included. The chemical scheme in the model includes 49 compounds, 101 reactions, and 16 photolytic reactions. The trace gas concentrations are calculated every 30 min, using a quasi steady state approximation. Model calculations of three cases are reported and compared. Enhanced methane concentration will have strongest effect in remote regions. In polluted areas local chemistry will have remarked effect. The feedback was always positive. Average atmospheric lifetime calculated in the model was 7.6 years, which agrees with recent estimates based on observations. 8 refs.

Catalytic properties of new anode materials for solid oxide fuel cells operated under methane at intermediary temperature

Science.gov (United States)

Sauvet, A.-L.; Fouletier, J.

The recent trend in solid oxide fuel cell concerns the use of natural gas as fuel. Steam reforming of methane is a well-established process for producing hydrogen directly at the anode side. In order to develop new anode materials, the catalytic activities of several oxides for the steam reforming of methane were characterized by gas chromatography. We studied the catalytic activity as a function of steam/carbon ratios r. The methane and the steam content were varied between 5 and 30% and between 1.5 and 3.5%, respectively, corresponding to r-values between 0.07 and 0.7. Catalyst (ruthenium and vanadium)-doped lanthanum chromites substituted with strontium, gadolinium-doped ceria (Ce 0.9Gd 0.1O 2) referred as to CeGdO 2, praseodymium oxide, molybdenum oxide and copper oxide were tested. The working temperature was fixed at 850°C, except for 5% ruthenium-doped La 1- xSr xCrO 3 where the temperature was varied between 700 and 850°C. Two types of behavior were observed as a function of the activity of the catalyst. The higher steam reforming efficiency was observed with 5% of ruthenium above 750°C.

Methane from dairy waste

Energy Technology Data Exchange (ETDEWEB)

1982-10-22

This short article describes a facility which will incorporate features to allow for the recovery of the methane gas that is produced in the manufacture of cheese and spray-dried whey powder at the site. The dairy plant is expected to produce about 1,385 m/sup 3//day of methane which will supplement the operation of oil burners and replace the annual consumption of 4,000 bbl of heavy fuel oil. In addition, development of the treatment system would eliminate the consumption of 7,200 kWh/day of electrical energy that would otherwise be required to operate an aerobic disposal system. Total annual energy savings, when the project is fully operational in the spring of 1984, are expected to reach $321,000.

The influence of incorporating MgO into Ni-based cermets by plasma spraying on anode microstructural and chemical stability in dry methane

Science.gov (United States)

Lay, E.; Metcalfe, C.; Kesler, O.

2012-11-01

The Solution Precursor Plasma Spray (SPPS) process was successfully used to deposit cermet coatings that exhibit fine microstructures with high surface area. MgO addition in Ni-YSZ and Ni-SDC cermets results in (Ni,Mg)O solid solution formation, and nickel particles after reduction are finer than in coatings without magnesia. The influence of MgO on the chemical stability of cermets in anodic operating conditions is discussed. It was found that a sufficient amount of magnesia addition (Ni0.9(MgO)0.1) helps to reduce carbon deposition in dry methane.

Vibrational Mode-Specific Reaction of Methane on a Nickel Surface

Science.gov (United States)

Beck, Rainer D.; Maroni, Plinio; Papageorgopoulos, Dimitrios C.; Dang, Tung T.; Schmid, Mathieu P.; Rizzo, Thomas R.

2003-10-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

Co-Fe-Si Aerogel Catalytic Honeycombs for Low Temperature Ethanol Steam Reforming

Directory of Open Access Journals (Sweden)

Montserrat Domínguez

2012-09-01

Full Text Available Cobalt talc doped with iron (Fe/Co~0.1 and dispersed in SiO2 aerogel was prepared from silica alcogel impregnated with metal nitrates by supercritical drying. Catalytic honeycombs were prepared following the same procedure, with the alcogel synthesized directly over cordierite honeycomb pieces. The composite aerogel catalyst was characterized by X-ray diffraction, scanning electron microscopy, focus ion beam, specific surface area and X-ray photoelectron spectroscopy. The catalytic layer is about 8 µm thick and adheres well to the cordierite support. It is constituted of talc layers of about 1.5 µm × 300 nm × 50 nm which are well dispersed and anchored in a SiO2 aerogel matrix with excellent mass-transfer properties. The catalyst was tested in the ethanol steam reforming reaction, aimed at producing hydrogen for on-board, on-demand applications at moderate temperature (573–673 K and pressure (1–7 bar. Compared to non-promoted cobalt talc, the catalyst doped with iron produces less methane as byproduct, which can only be reformed at high temperature, thereby resulting in higher hydrogen yields. At 673 K and 2 bar, 1.04 NLH2·mLEtOH(l−1·min−1 are obtained at S/C = 3 and W/F = 390 g·min·molEtOH−1.

Diurnal patterns of methane flux from a seasonal wetland: mechanisms and methodology

Science.gov (United States)

Bansal, Sheel; Tangen, Brian; Finocchiaro, Raymond

2018-01-01

Methane emissions from wetlands are temporally dynamic. Few chamber-based studies have explored diurnal variation in methane flux with high temporal replication. Using an automated sampling system, we measured methane flux every 2.5 to 4 h for 205 diel cycles during three growing seasons (2013–2015) from a seasonal wetland in the Prairie Pothole Region of North America. During ponded conditions, fluxes were generally positive (i.e., methanogenesis dominant, 10.1 ± 0.8 mg m−2 h−1), had extreme range of variation (from −1 to 70 mg m−2 h−1), and were highest during late day. In contrast, during dry conditions fluxes were very low and primarily negative (i.e., oxidation dominant, −0.05 ± 0.002 mg m−2 h−1), with the highest (least negative) fluxes occurring at pre-dawn. During semi-saturated conditions, methane fluxes also were very low, oscillated between positive and negative values (i.e., balanced between methanogenesis and methane oxidation), and exhibited no diel pattern. Methane flux was positively correlated with air temperature during ponded conditions (r = 0.57) and negatively during dry conditions (r = −0.42). Multiple regression analyses showed that temperature, light and water-filled pore space explained 72% of variation in methane flux. Methane fluxes are highly temporally dynamic and follow contrasting diel patterns that are dependent on dominant microbial processes influenced by saturation state.

Methane-free biogas for direct feeding of solid oxide fuel cells

Science.gov (United States)

Leone, P.; Lanzini, A.; Santarelli, M.; Calì, M.; Sagnelli, F.; Boulanger, A.; Scaletta, A.; Zitella, P.

This paper deals with the experimental analysis of the performance and degradation issues of a Ni-based anode-supported solid oxide fuel cell fed by a methane-free biogas from dark-anaerobic digestion of wastes by pastry and fruit shops. The biogas is produced by means of an innovative process where the biomass is fermented with a pre-treated bacteria inoculum (Clostridia) able to completely inhibit the methanization step during the fermentation process and to produce a H 2/CO 2 mixture instead of conventional CH 4/CO 2 anaerobic digested gas (bio-methane). The proposed biogas production route leads to a biogas composition which avoids the need of introducing a reformer agent into or before the SOFC anode in order to reformate it. In order to analyse the complete behaviour of a SOFC with the bio-hydrogen fuel, an experimental session with several H 2/CO 2 synthetic mixtures was performed on an anode-supported solid oxide fuel cell with a Ni-based anode. It was found that side reactions occur with such mixtures in the typical thermodynamic conditions of SOFCs (650-800 °C), which have an effect especially at high currents, due to the shift to a mixture consisting of hydrogen, carbon monoxide, carbon dioxide and water. However, cells operated with acceptable performance and carbon deposits (typical of a traditional hydrocarbon-containing biogas) were avoided after 50 h of cell operation even at 650 °C. Experiments were also performed with traditional bio-methane from anaerobic digestion with 60/40 vol% of composition. It was found that the cell performance dropped after few hours of operation due to the formation of carbon deposits. A short-term test with the real as-produced biogas was also successfully performed. The cell showed an acceptable power output (at 800 °C, 0.35 W cm -2 with biogas, versus 0.55 W cm -2 with H 2) although a huge quantity of sulphur was present in the feeding fuel (hydrogen sulphide at 103 ppm and mercaptans up to 10 ppm). Therefore, it

Methane-free biogas for direct feeding of solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Leone, P.; Lanzini, A.; Santarelli, M.; Cali, M. [Dipartimento di Energetica, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Turin (Italy); Sagnelli, F.; Boulanger, A.; Scaletta, A.; Zitella, P. [BioEnergy Lab, Environment Park S.p.A., Via Livorno 60, 10144 Turin (Italy)

2010-01-01

This paper deals with the experimental analysis of the performance and degradation issues of a Ni-based anode-supported solid oxide fuel cell fed by a methane-free biogas from dark-anaerobic digestion of wastes by pastry and fruit shops. The biogas is produced by means of an innovative process where the biomass is fermented with a pre-treated bacteria inoculum (Clostridia) able to completely inhibit the methanization step during the fermentation process and to produce a H{sub 2}/CO{sub 2} mixture instead of conventional CH{sub 4}/CO{sub 2} anaerobic digested gas (bio-methane). The proposed biogas production route leads to a biogas composition which avoids the need of introducing a reformer agent into or before the SOFC anode in order to reformate it. In order to analyse the complete behaviour of a SOFC with the bio-hydrogen fuel, an experimental session with several H{sub 2}/CO{sub 2} synthetic mixtures was performed on an anode-supported solid oxide fuel cell with a Ni-based anode. It was found that side reactions occur with such mixtures in the typical thermodynamic conditions of SOFCs (650-800 C), which have an effect especially at high currents, due to the shift to a mixture consisting of hydrogen, carbon monoxide, carbon dioxide and water. However, cells operated with acceptable performance and carbon deposits (typical of a traditional hydrocarbon-containing biogas) were avoided after 50 h of cell operation even at 650 C. Experiments were also performed with traditional bio-methane from anaerobic digestion with 60/40 vol% of composition. It was found that the cell performance dropped after few hours of operation due to the formation of carbon deposits. A short-term test with the real as-produced biogas was also successfully performed. The cell showed an acceptable power output (at 800 C, 0.35 W cm{sup -2} with biogas, versus 0.55 W cm{sup -2} with H{sub 2}) although a huge quantity of sulphur was present in the feeding fuel (hydrogen sulphide at 103 ppm and

Dry anaerobic digestion of lignocellulosic and protein residues

Directory of Open Access Journals (Sweden)

Maryam M Kabir

2015-12-01

Full Text Available Utilisation of wheat straw and wool textile waste in dry anaerobic digestion (AD process was investigated. Dry-AD of the individual substrates as well as co-digestion of those were evaluated using different total solid (TS contents ranging between 6 to 30%. Additionally, the effects of the addition of nutrients and cellulose- or protein-degrading enzymes on the performance of the AD process were also investigated. Dry-AD of the wheat straw resulted in methane yields of 0.081 – 0.200 Nm3CH4/kgVS with the lowest and highest values obtained at 30 and 21% TS, respectively. The addition of the cellulolytic enzymes could significantly increase the yield in the reactor containing 13% TS (0.231 Nm3CH4/kg VS. Likewise, degradation of wool textile waste was enhanced significantly at TS of 13% with the addition of the protein-degrading enzyme (0.131 Nm3CH4/kg VS. Furthermore, the co-digestion of these two substrates showed higher methane yields compared with the methane potentials calculated for the individual fractions at all the investigated TS contents due to synergetic effects and better nutritional balance.

Feasability of the direct generation of hydrogen for fuel-cell-powered vehicles by on-board steam reforming of naphta

NARCIS (Netherlands)

Darwish, Naif A.; Hilal, Nidal; Versteeg, Geert; Heesink, Albertus B.M.

2004-01-01

A process flow sheet for the production of hydrogen to run a 50 kW fuel-cell-powered-vehicle by steam reforming of naphtha is presented. The major units in the flow sheet involve a desulfurization unit, a steam reformer, a low temperature (LT) shift reactor, a methanation reactor, and a membrane

Feasibility of the direct generation of hydrogen for fuel-cell-powered vehicles by on-board steam reforming of naphtha

NARCIS (Netherlands)

Darwish, Naif A.; Hilal, Nidal; Versteeg, Geert; Heesink, Bert

2004-01-01

A process flow sheet for the production of hydrogen to run a 50 kW fuel-cell-powered-vehicle by steam reforming of naphtha is presented. The major units in the flow sheet involve a desulfurization unit, a steam reformer, a low temperature (LT) shift reactor, a methanation reactor, and a membrane

Membrane reforming in converting natural gas to hydrogen: Production costs, Part II

Energy Technology Data Exchange (ETDEWEB)

Iaquaniello, G; Cosenza, S [Technip-KTI S.p.A., via Castello della Magliana 75, Rome (Italy); Giacobbe, F; Morico, B; Farace, A [Processi Innovativi s.r.l., L' Aquila (Italy)

2008-11-15

This paper evaluates the production costs of a hybrid system based on a new membrane reforming MRR concept to convert natural gas to hydrogen and electricity. Membrane reforming with hydrogen-selective, palladium-silver membranes pushes the chemical equilibrium and allows higher methane conversions at lower temperature such as 650 C. The new MRR concept formed of a series of modules is put forward herein. Each module is made up of a reforming step and an external membrane separation unit. The estimates, based on utilities costs of a typical Italian refinery (end of 2006), show that the production costs for the hybrid system are 30% less than conventional tubular steam reforming technology, and 13% less than a gas-fired cogeneration plant coupled with a conventional H{sub 2} plant. (author)

Design of the steam reformer for the HTR-10 high temperature process heat application

International Nuclear Information System (INIS)

Ju Huaiming; Xu Yuanhui; Jia Haijun

2000-01-01

The 10 MW High Temperature Reactor Test Module (HTR-10) is being constructed now and planned to be operational in 2000. One of the objectives is to develop the high temperature process heat application. The methane steam reformer is one of the key-facilities for the nuclear process heat application system. The paper describes the conceptual design of the HTR-10 Steam Reformer with He heating, and the design optimization computer code. It can be used to perform sensitivity analysis for parameters, and to improve the design. Principal parameters and construction features of the HTR-10 reformer heated by He are introduced. (author)

Comparative study between fluidized bed and fixed bed reactors in methane reforming with CO2 and O2 to produce syngas

International Nuclear Information System (INIS)

Jing Qiangshan; Lou Hui; Mo Liuye; Zheng Xiaoming

2006-01-01

Reforming of methane with carbon dioxide and oxygen was investigated over Ni/MgO-SiO 2 catalysts using fixed bed and fluidized bed reactors. The conversions of CH 4 and CO 2 in a fluidized bed reactor were close to thermodynamic equilibrium. The activity and stability of the catalyst in the fixed bed reactor were lower than that in the fluidized bed reactor due to carbon deposition and nickel sintering. TGA and TEM techniques were used to characterize the spent catalysts. The results showed that a lot of whisker carbon was found on the catalyst in the rear of the fixed bed reactor, and no deposited carbon was observed on the catalysts in the fluidized bed reactor after reaction. It is suggested that this phenomenon is related to a permanent circulation of catalyst particles between the oxygen rich and oxygen free zones. That is, fluidization of the catalysts in the fluidized bed reactor favors inhibiting deposited carbon and thermal uniformity in the reactor

Methods for Detecting Microbial Methane Production and Consumption by Gas Chromatography.

Science.gov (United States)

Aldridge, Jared T; Catlett, Jennie L; Smith, Megan L; Buan, Nicole R

2016-04-05

Methane is an energy-dense fuel but is also a greenhouse gas 25 times more detrimental to the environment than CO 2 . Methane can be produced abiotically by serpentinization, chemically by Sabatier or Fisher-Tropsh chemistry, or biotically by microbes (Berndt et al. , 1996; Horita and Berndt, 1999; Dry, 2002; Wolfe, 1982; Thauer, 1998; Metcalf et al. , 2002). Methanogens are anaerobic archaea that grow by producing methane gas as a metabolic byproduct (Wolfe, 1982; Thauer, 1998). Our lab has developed and optimized three different gas chromatograph-utilizing assays to characterize methanogen metabolism (Catlett et al. , 2015). Here we describe the end point and kinetic assays that can be used to measure methane production by methanogens or methane consumption by methanotrophic microbes. The protocols can be used for measuring methane production or consumption by microbial pure cultures or by enrichment cultures.

High-temperature conversion of methane on a composite gadolinia-doped ceria-gold electrode

DEFF Research Database (Denmark)

Marina, O.A.; Mogensen, Mogens Bjerg

1999-01-01

Direct electrochemical oxidation of methane was attempted on a gadolinia-doped ceria Ce(0.6)Gd(0.4)O(1.8) (CG4) electrode in a solid oxide fuel cell using a porous gold-CG4 mixture as current collector Gold is relatively inert to methane in contrast to other popular SOFC anode materials such as n......Direct electrochemical oxidation of methane was attempted on a gadolinia-doped ceria Ce(0.6)Gd(0.4)O(1.8) (CG4) electrode in a solid oxide fuel cell using a porous gold-CG4 mixture as current collector Gold is relatively inert to methane in contrast to other popular SOFC anode materials...... such as nickel and platinum. CG4 was found to exhibit a low electrocatalytic activity for methane oxidation as well as no significant reforming activity implying that the addition of an electrocatalyst or cracking catalyst to the CG4 anode is required for SOFC operating on methane. The methane conversion...... observed at the open-circuit potential and low anodic overpotentials seems to be due to thermal methane cracking in the gas phase and on the alumina surfaces in the cell housing. At high anodic overpotentials, at electrode potentials where oxygen evolution was expected to take place, the formation of CO(2...

Tailored reforming of n-dodecane in an aqueous discharge reactor

KAUST Repository

Zhang, Xuming

2016-03-24

Here, we present an original technical approach to simultaneously produce a tailored synthetic liquid fuel and a syngas. In an aqueous discharge reactor with gaseous bubbles, we reformed an emulsified n-dodecane/water mixture. The higher dielectric permittivity of the mixture facilitates electrical discharges that cause the electron impact dissociation of n-dodecane into alkyl and hydrogen radicals, while the addition of water also provides a steam-reforming environment inside the discharged bubbles. We added methane and carbon dioxide to the system because they dissociate into methyl and oxygen radicals, respectively, which prevent the alkyl-alkyl recombinations that result in the formation of long-chain hydrocarbons (HCs). Thus, we were able to control product selectivity by adding methane to increase the production of short-chain HCs and hydrogen gas or by adding carbon dioxide to increase the production of oxygenated fuels, such as 1-dodecanol. Using gas chromatography and gas chromatography-mass spectrometry we detail the compositions of both the synthetic liquid and the syngas, and we provide conceptual chemical mechanisms to selectively increase the production of oxygenates and that of HCs that are shorter or longer than the base fuel. The basis of this in-liquid discharge for the purpose of fuel reforming has potential applications to advanced engines to control ignition delay time, a continuing focus of study in our lab. © 2016 IOP Publishing Ltd.

Hydrogen generator, via catalytic partial oxidation of methane for fuel cells

Science.gov (United States)

Recupero, Vincenzo; Pino, Lidia; Di Leonardo, Raffaele; Lagana', Massimo; Maggio, Gaetano

It is well known that the most acknowledged process for generation of hydrogen for fuel cells is based upon the steam reforming of methane or natural gas. A valid alternative could be a process based on partial oxidation of methane, since the process is mildly exothermic and therefore not energy intensive. Consequently, great interest is expected from conversion of methane into syngas, if an autothermal, low energy intensive, compact and reliable process could be developed. This paper covers the activities, performed by the CNR Institute of Transformation and Storage of Energy (CNR-TAE), on theoretical and experimental studies for a compact hydrogen generator, via catalytic selective partial oxidation of methane, integrated with second generation fuel cells (EC-JOU2 contract). In particular, the project focuses the attention on methane partial oxidation via heterogeneous selective catalysts, in order to: demonstrate the basic catalytic selective partial oxidation of methane (CSPOM) technology in a subscale prototype, equivalent to a nominal output of 5 kWe; develop the CSPOM technology for its application in electric energy production by means of fuel cells; assess, by a balance of plant analysis, and a techno-economic evaluation, the potential benefits of the CSPOM for different categories of fuel cells.

Dry anaerobic co-digestion of food waste and cattle manure: Impact of total solids, substrate ratio and thermal pre treatment on methane yield and quality of biomanure.

Science.gov (United States)

Arelli, Vijayalakshmi; Begum, Sameena; Anupoju, Gangagni Rao; Kuruti, Kranti; S, Shailaja

2018-04-01

The objective of the present study is to assess the impact of TS concentration, substrate mixing ratio (co digestion) and thermal pretreatment on biogas production, methane yield, VS reduction (%) and quality of biomanure through dry anaerobic digestion (DAD) of food waste (FW) and cattle manure (CM). Results divulged that the optimum methane yield and biomanure of 0.18 and 0.21 m 3 CH 4 /(kg VS reduced) and 3.15 and 2.8 kg/kg waste was obtained from FW at TS of 25% and 30% at an HRT of 41 and 31 days respectively whereas it was 0.32 and 0.43 m 3 CH 4 /(kg VS reduced) and 2.2 and 1.15 kg/kg waste from pretreated FW at an HRT of 16 and 20 days correspondingly. Improvement of methane from 62 to 81% was obtained due to thermal pretreatment. The highest nutrient recovery in terms of N, P, K was found to be 5.14, 2.6 and 3.2 respectively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synthesis and Application of Cerium-Incorporated SBA-16 Supported Ni-Based Oxygen Carrier in Cyclic Chemical Looping Steam Methane Reforming

Directory of Open Access Journals (Sweden)

Maryam Meshksar

2018-01-01

Full Text Available Hydrogen, as a clean energy carrier, could be produced aided by cyclic oxidation-reduction of oxygen carriers (OCs in contact with carbonaceous fuel in chemical looping steam methane reforming (CL-SMR process. In this study, the cerium was incorporated into the SBA-16 support structure to synthesize the Ni/Ce-SBA-16 OC. The supports were synthesized using hydrothermal method followed by impregnation of Ni and characterized via low and wide angle X-ray diffraction (XRD, Brunauer-Emmett-Teller (BET, scanning electron microscopy (SEM, coupled with energy dispersive X-ray (EDX spectroscopy, and transmission electron micrograph (TEM techniques. In addition, the effect of various Si/Ce molar ratios (20–60 in the support structure, Ni loading (10–30 wt %, reaction temperature (500–750 °C, and life time of optimal oxygen carrier over 16 cycles were investigated. The results of wide angle XRD and SEM revealed that the incorporation of CeO2 in the channels of SBA-16 caused the formation of nickel metallic particles with smaller size and prevents the coke formation. The results showed that OC with 15 wt % Ni and Si/Ce molar ratio of 40 (15Ni/Ce-SBA-16(40 has the best performance when compared with other OCs in terms of catalytic activity and structural properties. The methane conversion of about 99.7% was achieved at 700 °C using 15Ni/Ce-SBA-16(40 OC. We anticipate that the strategy can be extended to investigate a variety of novel modified mesoporous silica as the supporting material for the Ni based OCs.

A numerical simulation study on active species production in dense methane-air plasma discharge

Science.gov (United States)

Gui, LI; Muyang, QIAN; Sanqiu, LIU; Huaying, CHEN; Chunsheng, REN; Dezhen, WANG

2018-01-01

Recently, low-temperature atmospheric pressure plasmas have been proposed as a potential type of ‘reaction carrier’ for the conversion of methane into value-added chemicals. In this paper, the multi-physics field coupling software of COMSOL is used to simulate the detailed discharge characteristics of atmospheric pressure methane-air plasma. A two-dimensional axisymmetric fluid model is constructed, in which 77 plasma chemical reactions and 32 different species are taken into account. The spatial density distributions of dominant charged ions and reactive radical species, such as {{{CH}}}4+, {{{CH}}}3+, {{{N}}}2+, {{{O}}}2+, H, O, CH3, and CH2, are presented, which is due to plasma chemical reactions of methane/air dissociation (or ionization) and reforming of small fragment radical species. The physicochemical mechanisms of methane dissociation and radical species recombination are also discussed and analyzed.

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

This project was focused on developing a catalytic means of producing H2 from raw, ground biomass, such as fast growing poplar trees, willow trees, or switch grass. The use of a renewable, biomass feedstock with minimal processing can enable a carbon neutral means of producing H2 in that the carbon dioxide produced from the process can be used in the environment to produce additional biomass. For economically viable production of H2, the biomass is hydrolyzed and then reformed without any additional purification steps. Any unreacted biomass and other byproduct streams are burned to provide process energy. Thus, the development of a catalyst that can operate in the demanding corrosive environment and presence of potential poisons is vital to this approach. The concept for this project is shown in Figure 1. The initial feed is assumed to be a >5 wt% slurry of ground wood in dilute base, such as potassium carbonate (K2CO3). Base hydrolysis and reforming of the wood is carried out at high but sub-critical pressures and temperatures in the presence of a solid catalyst. A Pd alloy membrane allows the continuous removal of pure , while the retentate, including methane is used as fuel in the plant. The project showed that it is possible to economically produce H2 from woody biomass in a carbon neutral manner. Technoeconomic analyses using HYSYS and the DOE's H2A tool [1] were used to design a 2000 ton day-1 (dry basis) biomass to hydrogen plant with an efficiency of 46% to 56%, depending on the mode of operation and economic assumptions, exceeding the DOE 2012 target of 43%. The cost of producing the hydrogen from such a plant would be in the range of $1/kg H2 to $2/kg H2. By using raw biomass as a feedstock, the cost of producing hydrogen at large biomass consumption rates is more cost effective than steam reforming of hydrocarbons or biomass gasification and can achieve the overall cost goals of the DOE Fuel Cell Technologies Program. The complete conversion of wood

Effect of total solids content on methane and volatile fatty acid production in anaerobic digestion of food waste.

Science.gov (United States)

Liotta, Flavia; d'Antonio, Giuseppe; Esposito, Giovanni; Fabbricino, Massimiliano; van Hullebusch, Eric D; Lens, Piet N L; Pirozzi, Francesco; Pontoni, Ludovico

2014-10-01

This work investigates the role of the moisture content on anaerobic digestion of food waste, as representative of rapidly biodegradable substrates, analysing the role of volatile fatty acid production on process kinetics. A range of total solids from 4.5% to 19.2% is considered in order to compare methane yields and kinetics of reactors operated under wet to dry conditions. The experimental results show a reduction of the specific final methane yield of 4.3% and 40.8% in semi-dry and dry conditions compared with wet conditions. A decreasing trend of the specific initial methane production rate is observed when increasing the total solids concentration. Because of lack of water, volatile fatty acids accumulation occurs during the first step of the process at semi-dry and dry conditions, which is considered to be responsible for the reduction of process kinetic rates. The total volatile fatty acids concentration and speciation are proposed as indicators of process development at different total solids content. © The Author(s) 2014.

Methane and Root Dynamics in Arctic Soil

DEFF Research Database (Denmark)

D'Imperio, Ludovica

on the global climate. We investigated two aspects of arctic ecosystem dynamics which are not well represented in climatic models: i) soil methane (CH4) oxidation in dry heath tundra and barren soils and ii) root dynamics in wetlands. Field measurements were carried out during the growing season in Disko Island...

Effect of temperature on continuous dry fermentation of swine manure.

Science.gov (United States)

Deng, Liangwei; Chen, Chuang; Zheng, Dan; Yang, Hongnan; Liu, Yi; Chen, Ziai

2016-07-15

Laboratory-scale experiments were performed on the dry digestion of solid swine manure in a semi-continuous mode using 4.5 L down plug-flow anaerobic reactors with an organic loading rate of 3.46 kg volatile solids (VS) m(-3) d(-1) to evaluate the effects of temperature (15, 25 and 35 °C). At 15 °C, biogas production was the poorest due to organic overload and acidification, with a methane yield of 0.036 L CH4 g(-1) VS added and a volumetric methane production rate of 0.125 L CH4 L(-1) d(-1). The methane yield and volumetric methane production rate at 25 °C (0.226 L CH4 g(-1) VS added and 0.783 L CH4 L(-1) d(-1), respectively) were 6.24 times higher than those at 15 °C. However, the methane yield (0.237 L CH4 g(-1) VS added) and the volumetric methane production rate (0.821 L CH4 L(-1) d(-1)) at 35 °C were only 4.86% higher than those at 25 °C, which indicated similar results were obtained at 25 °C and 35 °C. The lower biogas production at 35 °C in dry digestion compared with that in wet digestion could be attributed to ammonia inhibition. For a single pig farm, digestion of solid manure is accomplished in small-scale domestic or small-farm bioreactors, for which operating temperatures of 35 °C are sometimes difficult to achieve. Considering biogas production, ammonia inhibition and net energy recovery, an optimum temperature for dry digestion of solid swine manure is 25 °C. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydrogen production via autothermal reforming of Diesel fuel

Energy Technology Data Exchange (ETDEWEB)

Pasel, J.; Meissner, J.; Pors, Z.; Cremer, P.; Peters, R.; Stolten, D. [Forschungszentrum Juelich GmbH, Institute for Materials and Processes in Energy Systems (IWV 3), D-52425 Juelich (Germany); Palm, C. [BASF Schwarzheide GmbH, Schipkauer Str. 1, Einheit PFO/I, D-01986 Schwarzheide (Germany)

2004-08-01

Hydrogen, for the operation of a polymer electrolyte fuel cell, can be produced by means of autothermal reforming of liquid hydrocarbons. Experiments, especially with ATR 4, which produces a molar hydrogen stream equivalent to an electrical power in the fuel cell of 3 kW, showed that the process should be preferably run in the temperature range between 700 and 850 . This ensures complete hydrocarbon conversion and avoids the formation of considerable amounts of methane and organic compounds in the product water. Experiments with commercial diesel showed promising results but insufficient long-term stability. Experiments concerning the ignition of the catalytic reaction inside the reformer proved that within 60 s after the addition of water and hydrocarbons the reformer reached 95% of its maximum molar hydrogen flow. Measurements, with respect to reformer start-up, showed that it takes approximately 7 min. to heat up the monolith to a temperature of 340 using an external heating device. Modelling is performed, aimed at the modification of the mixing chamber of ATR Type 5, which will help to amend the homogeneous blending of diesel fuel with air and water in the mixing chamber. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

Influence of rumen protozoa on methane emission in ruminants: a meta-analysis approach.

Science.gov (United States)

Guyader, J; Eugène, M; Nozière, P; Morgavi, D P; Doreau, M; Martin, C

2014-11-01

A meta-analysis was conducted to evaluate the effects of protozoa concentration on methane emission from ruminants. A database was built from 59 publications reporting data from 76 in vivo experiments. The experiments included in the database recorded methane production and rumen protozoa concentration measured on the same groups of animals. Quantitative data such as diet chemical composition, rumen fermentation and microbial parameters, and qualitative information such as methane mitigation strategies were also collected. In the database, 31% of the experiments reported a concomitant reduction of both protozoa concentration and methane emission (g/kg dry matter intake). Nearly all of these experiments tested lipids as methane mitigation strategies. By contrast, 21% of the experiments reported a variation in methane emission without changes in protozoa numbers, indicating that methanogenesis is also regulated by other mechanisms not involving protozoa. Experiments that used chemical compounds as an antimethanogenic treatment belonged to this group. The relationship between methane emission and protozoa concentration was studied with a variance-covariance model, with experiment as a fixed effect. The experiments included in the analysis had a within-experiment variation of protozoa concentration higher than 5.3 log10 cells/ml corresponding to the average s.e.m. of the database for this variable. To detect potential interfering factors for the relationship, the influence of several qualitative and quantitative secondary factors was tested. This meta-analysis showed a significant linear relationship between methane emission and protozoa concentration: methane (g/kg dry matter intake)=-30.7+8.14×protozoa (log10 cells/ml) with 28 experiments (91 treatments), residual mean square error=1.94 and adjusted R 2=0.90. The proportion of butyrate in the rumen positively influenced the least square means of this relationship.

Anaerobic digestion performance of sweet potato vine and animal manure under wet, semi-dry, and dry conditions.

Science.gov (United States)

Zhang, Enlan; Li, Jiajia; Zhang, Keqiang; Wang, Feng; Yang, Houhua; Zhi, Suli; Liu, Guangqing

2018-03-22

Sweet potato vine (SPV) is an abundant agricultural waste, which is easy to obtain at low cost and has the potential to produce clean energy via anaerobic digestion (AD). The main objectives of this study were to reveal methane production and process stability of SPV and the mixtures with animal manure under various total solid conditions, to verify synergetic effect in co-digestion of SPV and manure in AD systems, and to determine the kinetics characteristics during the full AD process. The results showed that SPV was desirable feedstock for AD with 200.22 mL/g VS added of methane yield in wet anaerobic digestion and 12.20 L methane /L working volume in dry anaerobic digestion (D-AD). Synergistic effects were found in semi-dry anaerobic digestion and D-AD with each two mixing feedstock. In contrast with SPV mono-digestion, co-digestion with manure increased methane yield within the range of 14.34-49.11% in different AD digesters. The values of final volatile fatty acids to total alkalinity (TA) were below 0.4 and the values of final pH were within the range of 7.4-8.2 in all the reactors, which supported a positive relationship between carbohydrate hydrolysis and methanogenesis during AD process. The mathematical modified first order model was applied to estimate substrate biodegradability and methane production potential well with conversion constant ranged from 0.0003 to 0.0953 1/day, which indicated that co-digestion increased hydrolysis efficiency and metabolic activity. This work provides useful information to improve the utilization and stability of digestion using SPV and livestock or poultry manure as substrates.

Can rapeseed lower methane emission from heifers?

DEFF Research Database (Denmark)

Hellwing, Anne Louise Frydendahl; Sørensen, Martin Tang; Weisbjerg, Martin Riis

2013-01-01

Twelve heifers were assigned to either a control diet (CON) with 26 g fat per kg dry matter (DM) or a supplemented diet (FAT) with crushed rapeseed with 53 g fat per kg DM. Methane (CH4) emission was measured by open-circuit indirect calorimetry for four days when the heifers weighed approximately...

Pd-Ag membrane reactor for steam reforming reactions: a comparison between different fuels

NARCIS (Netherlands)

Gallucci, F.; Basile, A.

2008-01-01

The simulation of a dense Pd-based membrane reactor for carrying out the methane, the methanol and the ethanol steam reforming (SR) reactions for pure hydrogen production is performed. The same simulation is also performed in a traditional reactor. This modelling work shows that the use of membrane

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.

Decomposition of methane hydrate for hydrogen production using microwave and radio frequency in-liquid plasma methods

International Nuclear Information System (INIS)

Rahim, Ismail; Nomura, Shinfuku; Mukasa, Shinobu; Toyota, Hiromichi

2015-01-01

This research involves two in-liquid plasma methods of methane hydrate decomposition, one using radio frequency wave (RF) irradiation and the other microwave radiation (MW). The ultimate goal of this research is to develop a practical process for decomposition of methane hydrate directly at the subsea site for fuel gas production. The mechanism for methane hydrate decomposition begins with the dissociation process of methane hydrate formed by CH_4 and water. The process continues with the simultaneously occurring steam methane reforming process and methane cracking reaction, during which the methane hydrate is decomposed releasing CH_4 into H_2, CO and other by-products. It was found that methane hydrate can be decomposed with a faster rate of CH_4 release using microwave irradiation over that using radio frequency irradiation. However, the radio frequency plasma method produces hydrogen with a purity of 63.1% and a CH conversion ratio of 99.1%, which is higher than using microwave plasma method which produces hydrogen with a purity of 42.1% and CH_4 conversion ratio of 85.5%. - Highlights: • The decomposition of methane hydrate is proposed using plasma in-liquid method. • Synthetic methane hydrate is used as the sample for decomposition in plasma. • Hydrogen can be produced from decomposition of methane hydrate. • Hydrogen purity is higher when using radio frequency stimulation.

Methane distributions and transports in the nocturnal boundary layer at a rural station

Science.gov (United States)

Schäfer, Klaus; Zeeman, Matthias; Brosy, Caroline; Münkel, Christoph; Fersch, Benjamin; Mauder, Matthias; Emeis, Stefan

2016-10-01

To investigate the methane distributions and transports, the role of related atmospheric processes by determination of vertical profiles of wind, turbulence, temperature and humidity as well as nocturnal boundary layer (NBL) height and the quantification of methane emissions at local and plot scale the so-called ScaleX-campaign was performed in a pre-alpine observatory in Southern Germany from 01 June until 31 July 2015. The following measurements from the ground up to the free troposphere were performed: layering of the atmosphere by a ceilometer (Vaisala CL51); temperature, wind, turbulence profiles from 50 m up to 500 m by a Radio-Acoustic Sounding System (RASS, Metek GmbH); temperature, humidity profiles in situ by a hexacopter; methane farm emissions by two open-path laser spectrometers (Boreal GasFinder2); methane concentrations in situ (Los Gatos DLT-100) with tubes in 0.3 m agl and 5 sampling heads; and methane soil emissions by a big chamber (10 m length, 2.60 m width, up to 0.61 m height) with a plastic cover. The methane concentrations near the surface show a daily variation with a maximum and a frequent double-peak structure during night-time. Analysis of the variation of the nocturnal methane concentration together with the hexacopter and RASS data indicates that the first peak in the nocturnal methane concentration is probably due to local cooling and stabilization which keeps the methane emissions from the soil near the ground. The second peak seems to be due to advection of methane-enriched air which had formed in the environment of the nearby farm yards. These dairy farm emissions were determined by up-wind and down-wind open-path concentration measurements, turbulence data from an EC station nearby and Backward Lagrangian Simulation (WindTrax software). The methane fluxes at plot scale (big chamber) are characterized by emissions at water saturated grassland patches, by an exponential decrease of these emissions during grassland drying, and by an

Heat and mass transfer in a reforming catalyst bed. Analytical prediction of distributions in the catalyst bed; Kaishitsu shokubaiso ni okeru netsu oyobi busshitsu ido. Suchi kaiseki ni yoru sonai bunpu no yosoku

Energy Technology Data Exchange (ETDEWEB)

Usami, Y [Tokyo Electric Power Co. Inc., Tokyo (Japan); Fukusako, S; Yamada, M [Hokkaido University, Sapporo (Japan)

2000-01-25

Heat and mass transfer characteristics within a reforming catalyst bed have been analytically investigated. A numerical analysis was carried out in a two-dimensional steady-state model of reforming catalyst layer. Reforming tube was filled with catalyst and the tube wall was uniformly heated, a mixture of steam and methane was reformed through the catalyst bed. Predicted temperature, formed gas composition, methane conversion rate, and heat transfer coefficient distributions in the catalyst layer showed good agreement with experimental data. The effects of space velocity, steam carbon molar ratio, and wall temperature on the heat transfer coefficient were analytically presented. From temperature and composition distributions simulated by two-dimensional analysis, the effects of these factors above mentioned and diffusion on the transport phenomena were qualitatively predicted. (author)

Hydrogen generation from biogenic and fossil fuels by autothermal reforming

Science.gov (United States)

Rampe, Thomas; Heinzel, Angelika; Vogel, Bernhard

Hydrogen generation for fuel cell systems by reforming technologies from various fuels is one of the main fields of investigation of the Fraunhofer ISE. Suitable fuels are, on the one hand, gaseous hydrocarbons like methane, propane but also, on the other hand, liquid hydrocarbons like gasoline and alcohols, e.g., ethanol as biogenic fuel. The goal is to develop compact systems for generation of hydrogen from fuel being suitable for small-scale membrane fuel cells. The most recent work is related to reforming according to the autothermal principle — fuel, air and steam is supplied to the reactor. Possible applications of such small-scale autothermal reformers are mobile systems and also miniature fuel cell as co-generation plant for decentralised electricity and heat generation. For small stand-alone systems without a connection to the natural gas grid liquid gas, a mixture of propane and butane is an appropriate fuel.

Chemical composition and methane potential of commercial food wastes.

Science.gov (United States)

Lopez, Victoria M; De la Cruz, Florentino B; Barlaz, Morton A

2016-10-01

There is increasing interest in anaerobic digestion in the U.S. However, there is little information on the characterization of commercial food waste sources as well as the effect of waste particle size on methane yield. The objective of this research was to characterize four commercial food waste sources: (1) university dining hall waste, (2) waste resulting from prepared foods and leftover produce at a grocery store, (3) food waste from a hotel and convention center, and (4) food preparation waste from a restaurant. Each sample was tested in triplicate 8L batch anaerobic digesters after shredding and after shredding plus grinding. Average methane yields for the university dining, grocery store, hotel, and restaurant wastes were 363, 427, 492, and 403mL/dry g, respectively. Starch exhibited the most complete consumption and particle size did not significantly affect methane yields for any of the tested substrates. Lipids represented 59-70% of the methane potential of the fresh substrates. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ground truthing for methane hotspots at Railroad Valley, NV - application to Mars

Science.gov (United States)

Detweiler, A. M.; Kelley, C. A.; Bebout, B.; McKay, C. P.; DeMarines, J.; Yates, E. L.; Iraci, L. T.

2011-12-01

During the 2010 Greenhouse gas Observing SATellite (GOSAT) calibration and validation campaign at Railroad Valley (RRV) playa, NV, unexpected methane and carbon dioxide fluctuations were observed at the dry lakebed. Possible sources included the presence of natural gas (thermogenic methane) from oil deposits in the surrounding playa, and/or methane production from microbial activity (biogenic) in the subsurface of the playa. In the summer of 2011, measurements were undertaken to identify potential methane sources at RRV. The biogenicity of the methane was determined based on δ13C values and methane/ethane ratios. Soil gas samples and sediments were collected at different sites in the playa and surrounding areas. The soils of the playa consist of a surface crust layer (upper ~ 10 cm) grading to a dense clay below about 25 cm. Soil gas from the playa, sampled at about 20 and 80 cm depths, reflected atmospheric methane concentrations, ranging from 2 to 2.4 ppm, suggesting that no methane was produced within the playa. Natural springs on the northeast and western border of the playa, detected as methane hotspots from a flyover by the Sensor Integrated Environmental Remote Research Aircraft (SIERRA), were also sampled. Bubbles in these springs had methane concentrations that ranged from 69 to 84% by volume. In addition, ethane was detected at very low concentrations, giving methane/ethane ratios in excess of 100,000, indicating biogenic methane in the springs. Soils and sediments collected at the playa and spring sites were incubated in vials over a period of ~23 days. Methane production was observed in the spring sites (avg. 228.6 ± 49.1 nmol/g/d at Kate Springs), but was not evident for the playa sites. The incubation data, therefore, corroborated in situ methane concentration measurements. Particulate organic carbon (POC) was low for all sites samples (0.05-0.38%), with the exception of Kate Springs, which had a much higher POC concentration of 3.4 ± 0

Status of a reformer design for a modular HTGR in an in-line configuration

International Nuclear Information System (INIS)

Gluck, R.; Whitling, W.H.; Lipps, A.J.

1984-01-01

For the past several years the General Electric Company has had the technical lead on advanced concept studies for the Modular High Temperature Gas Cooled Reactor (HTGR) programs sponsored by the United States Department of Energy. The focus of the Modular Reactor System (MRS) effort is the development of a generic nuclear heat source capable of supplying heat to either a steam generator/electric cycle or a high temperature steam /methane reforming cycle. Some early ground rules for this study were that the reactor be designed for 950 deg. C direct cycle reforming and that the core be of the prismatic type. Since the prismatic core required control rods near the center of the core, the vertical in-line concept was selected to promote natural circulation cooling of the core for all potential transients except the depressurized core heatup transient. Although the requirement for a prismatic core has been eliminated for recent cost reduction studies, the vertical in-line configuration has been retained for its potential as the lowest cost configuration. This paper presents the results of recent design and analytical studies conducted to evaluate the feasibility of using a steam/methane reformer in a Vertical In-Line (VIL) arrangement with the generic nuclear heat source

Climate change and energy policies, coal and coalmine methane in China

Energy Technology Data Exchange (ETDEWEB)

Yang Ming [3E and T International, Suite 1506, Building No. 10, Luo Ma Shi Street, Xuanwu District, Beijing 100052 (China)], E-mail: ming.yang7@gmail.com

2009-08-15

The Chinese government has made many energy policies on coal, and coalmine methane (CMM) use. However, not all of these policies have effects or positive impacts. For example, it has been quite a few years since the national government made policies to encourage coalmine methane power to be sold to the grid. Practice showed that not any kilowatt of electricity was sold from a coalmine methane power plant to the grid in Sichuan and Guizhou Provinces as of December 2008. The objectives of this paper are to review and evaluate the Chinese government energy and climate policies that are related to coal and coalmine methane, analyze relevant policy barriers, and make recommendations to overcome these barriers and avoid policy failures. This paper provides the literature review, challenges, resources, policies and other updated information on China's CMM recovery and utilization. The paper concludes that China needs to further reform its energy and environment management system, engage provincial governments in CMM capture and use activities, and provide incentives to qualified engineers and skilled workers to work in remote coal mining areas. This paper transfers key messages to policy makers for them to make better CMM capture and use policies.

Climate change and energy policies, coal and coalmine methane in China

International Nuclear Information System (INIS)

Yang Ming

2009-01-01

The Chinese government has made many energy policies on coal, and coalmine methane (CMM) use. However, not all of these policies have effects or positive impacts. For example, it has been quite a few years since the national government made policies to encourage coalmine methane power to be sold to the grid. Practice showed that not any kilowatt of electricity was sold from a coalmine methane power plant to the grid in Sichuan and Guizhou Provinces as of December 2008. The objectives of this paper are to review and evaluate the Chinese government energy and climate policies that are related to coal and coalmine methane, analyze relevant policy barriers, and make recommendations to overcome these barriers and avoid policy failures. This paper provides the literature review, challenges, resources, policies and other updated information on China's CMM recovery and utilization. The paper concludes that China needs to further reform its energy and environment management system, engage provincial governments in CMM capture and use activities, and provide incentives to qualified engineers and skilled workers to work in remote coal mining areas. This paper transfers key messages to policy makers for them to make better CMM capture and use policies.

In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

KAUST Repository

Al-Sabban, Bedour E.; Falivene, Laura; Kozlov, Sergey M.; Aguilar Tapia, Antonio; Ould-Chikh, Samy; Hazemann, Jean-Louis; Cavallo, Luigi; Basset, Jean-Marie; Takanabe, Kazuhiro

2017-01-01

Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals

Methane emissions from MBT landfills

Energy Technology Data Exchange (ETDEWEB)

Heyer, K.-U., E-mail: heyer@ifas-hamburg.de; Hupe, K.; Stegmann, R.

2013-09-15

Highlights: • Compilation of methane generation potential of mechanical biological treated (MBT) municipal solid waste. • Impacts and kinetics of landfill gas production of MBT landfills, approach with differentiated half-lives. • Methane oxidation in the waste itself and in soil covers. • Estimation of methane emissions from MBT landfills in Germany. - Abstract: Within the scope of an investigation for the German Federal Environment Agency (“Umweltbundesamt”), the basics for the estimation of the methane emissions from the landfilling of mechanically and biologically treated waste (MBT) were developed. For this purpose, topical research including monitoring results regarding the gas balance at MBT landfills was evaluated. For waste treated to the required German standards, a methane formation potential of approximately 18–24 m{sup 3} CH{sub 4}/t of total dry solids may be expected. Monitoring results from MBT landfills show that a three-phase model with differentiated half-lives describes the degradation kinetics in the best way. This is due to the fact that during the first years of disposal, the anaerobic degradation processes still proceed relatively intensively. In addition in the long term (decades), a residual gas production at a low level is still to be expected. Most of the soils used in recultivation layer systems at German landfills show a relatively high methane oxidation capacity up to 5 l CH{sub 4}/(m{sup 2} h). However, measurements at MBT disposal sites indicate that the majority of the landfill gas (in particular at non-covered areas), leaves the landfill body via preferred gas emission zones (hot spots) without significant methane oxidation. Therefore, rather low methane oxidation factors are recommended for open and temporarily covered MBT landfills. Higher methane oxidation rates can be achieved when the soil/recultivation layer is adequately designed and operated. Based on the elaborated default values, the First Order Decay (FOD

Chemical looping reforming of generator gas

Energy Technology Data Exchange (ETDEWEB)

Mendiara, T.; Jensen, Anker; Glarborg, P.

2010-02-15

The main objective of this work is to investigate the carbon deposition during reforming of hydrocarbons in a Chemical Looping Reformer (CLR). This knowledge is needed to asses the viability of the CLR technology in reforming tar from biomass gasification preserving lighter hydrocarbons and minimizing the carbon formation during the process. Two different setups were used to test the reactivity of the different samples in the conditions of interest for the tar reforming process: 1) Fixed bed flow reactor (FR), and 2) Thermogravimetric analyzer (TGA). In the experiments, the gas atmosphere was switched from reducing to oxidizing atmosphere in every cycle. During the oxidizing cycle, the carrier was regenerated using a mixture of oxygen and nitrogen. Four different oxygen carriers based on nickel (Ni40 and Ni60), manganese (Mn) and ilmenite (Fe) were tested. In the tests, toluene was used to simulate the tars. The Fe and the Mn carrier reacted to a small extent with methane at the highest temperature studied, 800 degrees C. The Ni-carriers did not react at 600 degrees C at first, but they showed some reactivity after having been activated at the higher temperature. Carbon formation occurred with the Ni-carriers, more so with the Ni60 than the Ni40. Ni40, Mn and Fe were activated at the higher temperature. However, Fe showed only low capacity. Ni60 showed no capability of tar reforming. Ni40 showed a high tendency to carbon formation at 800 degrees C, but the formation could be lowered by changing some parameters. Mn formed almost no carbon. Ni40 and Mn were chosen for further studies. Carbon deposition occurred for both Ni40 and Mn, but the amount deposited for Ni40 was about 10 times bigger. Ni40 reacted with the methane and toluene only at 800 degrees C. The conversion over Mn was not as big as for toluene alone. Carbon was formed from carbon monoxide on the Ni40 carrier and on the Mn, but to a much less extent on the latter one. The presence of hydrogen decreased

Analyses of one-step liquid hydrogen production from methane and landfill gas

Energy Technology Data Exchange (ETDEWEB)

Huang, Cunping; T-Raissi, Ali [University of Central Florida, Florida Solar Energy Center, 1679 Clearlake Road, Cocoa, FL 32922-5703 (United States)

2007-11-15

Conventional liquid hydrogen (LH{sub 2}) production consists of two basic steps: (1) gaseous hydrogen (GH{sub 2}) production via steam methane reformation followed by purification by means of pressure swing adsorption (PSA), and (2) GH{sub 2} liquefaction. LH{sub 2} produced by the conventional processes is not carbon neutral because of the carbon dioxide (CO{sub 2}) emission from PSA operation. A novel concept is herein presented and flowsheeted for LH{sub 2} production with zero carbon emission using methane (CH{sub 4}) or landfill gas as feedstock. A cryogenic process is used for both H{sub 2} separation/purification and liquefaction. This one-step process can substantially increase the efficiency and reduce costs because no PSA step is required. Furthermore, the integrated process results in no CO{sub 2} emissions and minimal H{sub 2} losses. Of the five flowsheets presented, one that combines low and high temperature CO/CH{sub 4} reforming reactions in a single reactor shows the highest overall efficiency with the first and second law efficiencies of 85% and 56%, respectively. The latter figure assumes 10% overall energy loss and 30% efficiency for the cryogenic process. (author)

The effect of gas permeation through vertical membranes on chemical switching reforming (CSR) reactor performance

NARCIS (Netherlands)

Wassie, S.A.; Gallucci, F.; Cloete, S.; Zaabout, A.; van Sint Annaland, M.; Amini, S.

2016-01-01

A novel membrane assisted fluidized bed reactor concept has been proposed for ultra-pure hydrogen production with integrated CO2 capture from steam methane reforming. The so-called Chemical Switching Reactor (CSR) concept combines the use of an oxygen carrier for supplying heat and catalysing the

Advanced design of fast reactor-membrane reformer (FR-MR)

International Nuclear Information System (INIS)

Tashimo, M.; Hori, I.; Yasuda, I.; Shirasaki, Y.; Kobayashi, K.

2004-01-01

A new plant concept of nuclear-produced hydrogen is being studied using a Fast Reactor-Membrane Reformer (FR-MR). The conventional steam methane reforming (SMR) system is a three-stage process. The first stage includes the reforming, the second contains a shift reaction and the third is the separation process. The reforming process requires high temperatures of 800 ∼ 900 deg C. The shift process generates heat and is performed at around 200 deg C. The membrane reforming has only one process stage under a nonequilibrium condition by removing H2 selectively through a membrane tube. The steam reforming temperature can be decreased from 800 deg C to 550 deg C, which is a remarkable benefit offered by the non-equilibrium condition. With this new technology, the reactor type can be changed from a High Temperature Gas-cooled Reactor (HTGR) to a Fast Reactor (FR). A Fast Reactor-Membrane Reformer (FR-MR) is composed of a nuclear plant and a hydrogen plant. The nuclear plant is a sodium-cooled Fast Reactor with mixed oxide fuel and with a power of 240 MWt. The heat transport system contains two circuits, the primary circuit and the secondary circuit. The membrane reformer units are set in the secondary circuit. The heat, supplied by the sodium, can produce 200 000 Nm 3 /h by 2 units. There are two types of membranes. One is made of Pd another one (advanced) is made of, for example V, or Nb. The technology for the Pd membrane is already established in a small scale. The non-Pd type is expected to improve the performance. (author)

AO13. High energy, low methane syngas from low-rank coals for coal-to-liquids production

Energy Technology Data Exchange (ETDEWEB)

Lucero, Andrew [Southern Research Institute, Durham, NC (United States); Goyal, Amit [Southern Research Institute, Durham, NC (United States); McCabe, Kevin [Southern Research Institute, Durham, NC (United States); Gangwal, Santosh [Southern Research Institute, Durham, NC (United States)

2015-06-30

An experimental program was undertaken to develop and demonstrate novel steam reforming catalysts for converting tars, C2+ hydrocarbons, and methane under high temperature and sulfur environments at lab scale. Several catalysts were developed and synthesized along with some catalysts based on recipes found in the literature. Of these, two had good resistance at 90 ppm H₂S with one almost not affected at all. Higher concentrations of H₂S did affect methane conversion across the catalyst, but performance was fairly stable for up to 200 hours. Based on the results of the experimental program, a techno-economic analysis was developed for IGCC and CTL applications and compared to DOE reference cases to examine the effects of the new technology. In the IGCC cases, the reformer/POX system produces nearly the same amount of electricity for nearly the same cost, however, the reformers/POX case sequesters a higher percentage of the carbon when compared to IGCC alone. For the CTL case the economics of the new process were nearly identical to the CTL case, but due to improved yields, the greenhouse gas emissions for a given production of fuels was approximately 50% less than the baseline case.

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

Science.gov (United States)

Li, Shuirong; Gong, Jinlong

2014-11-07

of other types of heterogeneous base-metal catalysts for high temperature processes including methanation, dry reforming, and hydrocarbon combustion.

Electrochemical Impedance Spectroscopy (EIS) Characterization of Reformate-operated High Temperature PEM Fuel Cell Stack

DEFF Research Database (Denmark)

Sahlin, Simon Lennart; Simon Araya, Samuel; Andreasen, Søren Juhl

2017-01-01

their effects on a reformate-operated stack. Polarization curves were also recorded to complement the impedance analysis of the researched phenomena. An equivalent circuit model was used to estimate the different resistances at varying parameters. It showed a significantly higher low frequency resistance......, λanode= 1.6 for reformate operation and λcathode= 4.The work also compared dry hydrogen, steam reforming and autothermal reforming gas feeds at160 ◦Cand showed appreciably lower performance in the case of autothermal reforming at the same stoichiometry, mainly attributable to mass transport related...

The EU's Agenda 2000 reform for the agricultural sector. Environmental and economic effects in Denmark

International Nuclear Information System (INIS)

Wier, Mette; Andersen, Johnny M.; Jensen, Joergen D.; Jensen, Thomas C.

2002-01-01

The Agenda 2000 reform, agreed on by the EU government leaders in the spring of 1999, implies considerable changes in EU agricultural policy. The reform involves both reductions in price support and compensations in the form of hectare and animal support. The Agenda 2000 reform may have considerable environmental and economic effects, and in this article we assess these effects. Within an integrated model system, we calculate environmental effects (changes in nitrogen loading in the terrestrial environment and the Danish marine waters, changes in oxygen concentrations in the inner Danish marine waters, and changes in emissions of the greenhouse gases (methane and nitrous oxide)), as well as economic effects (effects on private consumption, GDP, the balance of payments, and employment). The results indicate that the Agenda 2000 reform has significant economic costs but almost no effects on the environment - either positive or negative

Investigation on reactivity of iron nickel oxides in chemical looping dry reforming

International Nuclear Information System (INIS)

Huang, Zhen; He, Fang; Chen, Dezhen; Zhao, Kun; Wei, Guoqiang; Zheng, Anqing; Zhao, Zengli; Li, Haibin

2016-01-01

Iron nickel oxides as oxygen carriers were investigated to clarify the reaction mechanism of NiFe_2O_4 material during the chemical looping dry reforming (CLDR) process. The thermodynamic analysis showed that metallic Fe can be oxidized into Fe_3O_4 by CO_2, but metallic Ni cannot. The oxidizability of the four oxygen carriers was in the order of NiO > synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3, and the reducibility sequence of their reduced products was synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3 > NiO. The NiO showed the best oxidizability but it was easy to cause CH_4 cracking and its reduced product (Ni) did not recover lattice oxygen under CO_2 atmosphere. It only produced 74 mL CO for 1 g Fe_2O_3 during the CO_2 reforming because of its weak oxidizability. The Redox ability of synthetic NiFe_2O_4 was obvious higher than that of NiO-Fe_2O_3 mixed oxides due to the synergistic effect of metallic Fe-Ni in the spinel structure. 1 g synthetic NiFe_2O_4 can produce 238 mL CO, which was twice higher than that of 1 g NiO-Fe_2O_3 mixed oxides (111 mL). A part of Fe element was divorced from the NiFe_2O_4 spinel structure after one cycle, which was the major reason for degradation of reactivity of NiFe_2O_4 oxygen carrier. - Highlights: • A synergistic effect of Fe/Ni can improve the reactivity of oxygen carrier (OC). • The oxidizability sequence of four OCs is NiO > NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3. • The reducibility sequence of four OCs is NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3 > NiO. • The formation of Fe (Ni) alloy phase facilitates more CO_2 reduced into CO. • Part of Fe is divorced from the spinel structure, leading to the degeneration of OC reactivity.

Simulating the effects of grassland management and grass ensiling on methane emission from lactating cows

NARCIS (Netherlands)

Bannink, A.; Smits, M.C.J.; Kebreab, E.; Mills, J.A.N.; Ellis, J.L.; Klop, A.; France, J.; Dijkstra, J.

2010-01-01

A dynamic, mechanistic model of enteric fermentation was used to investigate the effect of type and quality of grass forage, dry matter intake (DMI) and proportion of concentrates in dietary dry matter (DM) on variation in methane (CH4) emission from enteric fermentation in dairy cows. The model

Hydrogen production from biomass pyrolysis gas via high temperature steam reforming process

International Nuclear Information System (INIS)

Wongchang, Thawatchai; Patumsawad, Suthum

2010-01-01

Full text: The aim of this work has been undertaken as part of the design of continuous hydrogen production using the high temperature steam reforming process. The steady-state test condition was carried out using syngas from biomass pyrolysis, whilst operating at high temperatures between 600 and 1200 degree Celsius. The main reformer operating parameters (e.g. temperature, resident time and steam to biomass ratio (S/B)) have been examined in order to optimize the performance of the reformer. The operating temperature is a key factor in determining the extent to which hydrogen production is increased at higher temperatures (900 -1200 degree Celsius) whilst maintaining the same as resident time and S/B ratio. The effects of exhaust gas composition on heating value were also investigated. The steam reforming process produced methane (CH 4 ) and ethylene (C 2 H 4 ) between 600 to 800 degree Celsius and enhanced production ethane (C 2 H 6 ) at 700 degree Celsius. However carbon monoxide (CO) emission was slightly increased for higher temperatures all conditions. The results show that the use of biomass pyrolysis gas can produce higher hydrogen production from high temperature steam reforming. In addition the increasing reformer efficiency needs to be optimized for different operating conditions. (author)

Simulation of Reforming Reactor Tube: Quantifying Catalyst Pellet's Effectiveness Factor

OpenAIRE

Da Cruz, Flavio Eduardo

2016-01-01

In this work, a consistent mathematical model to simulate a spherical catalytic pellet and a Packed-Bed Reactor (PBR) is develop. The Dusty Gas Model (DGM) is applied to the calculation of the diffusive fluxes in the porous media. Simulations are executed considering hydrogen production from steam methane reforming. Species’ diffusivities are calculated using data from literature as well as the values for tortuosity and porosity. The pellet simulation is performed considering mass, species, m...

Methane fluxes from a wet puna ecosystem in the Peruvian Andes

Science.gov (United States)

Jones, Sam; Diem, Torsten; Priscila Huaraca Quispe, Lidia; Quispe Ccahuana, Adan Julian; Meir, Patrick; Arn Teh, Yit

2014-05-01

Discrepancies exist between top-down and bottom-up estimates of the tropical South American atmospheric methane budget. This suggests that current source-sink inventories fail to adequately characterise the landscapes of the region. This may be particularly true of Andean environments where very few field observations have been made. The high tropical Andes, between tree and permanent snow-lines, is home to diverse grass, shrub and giant rosette dominated ecosystems known variously from Venezuela to northern Chile and Argentina as paramo, jalca and puna. In humid regions these are characterised by wet, organic-rich mineral soils, peat-forming wetlands and shallow lakes. Such conditions are likely to promote methane production and potentially represent a regionally significant source to the atmosphere that should be considered. We report on methane fluxes from a bunch-grass dominated puna habitat at 3500 m above sea level in south-eastern Peru. Mean annual temperature and precipitation are 11 °C and 2500 mm, respectively. Temperature is aseasonal but experiences considerable diurnal variations with overnight frosting common-place. In contrast, rainfall is intensely episodic and has a pronounced wet season between September and March. Sampling encompassed a range of topographic features, such as grassland on freely draining, gently inclined or steep slopes and depressions containing bogs, over a 3 ha ridge to basin transition. Monthly sampling was carried out between January 2011 and June 2013 to investigate seasonal variability in methane fluxes. Intensive sampling campaigns were conducted to investigate spatial and short-term variations on a daily basis in two nine-day campaigns during wet and dry season. The site was a net source of methane to the atmosphere during the period of study. Methane fluxes were dominated by emissions from bogs, whereas, freely draining grassland exhibited weak source or marginal sink activity. Temporal variations were most notable at

Creating Methane from Plastics: Recycling at a Lunar Outpost

Science.gov (United States)

Captain, Janine; Santiago, Eddie; Wheeler, Ray; Strayer, RIchard; Garland, Jay; Parrish, Clyde

2010-01-01

The high cost of re-supply from Earth demands resources to be utilized to the fullest extent for exploration missions. 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. The ability to refuel on the lunar surface would reduce the vehicle mass during launch and provide excess payload capability. The goal of this project is to determine the feasibility of recycling waste into methane on the lunar outpost by performing engineering assessments and lab demonstrations of the technology. The first goal of the project was to determine how recycling could influence lunar exploration. Table I shows an estimation of the typical dried waste stream generated each day for a crew of four. Packaging waste accounts for nearly 86% of the dry waste stream and is a significant source of carbon on the lunar surface. This is important because methane (CH4) can be used as fuel and no other source of carbon is available on the lunar surface. With the initial assessment indicating there is sufficient resources in the waste stream to provide refueling capabilities, the project was designed to examine the conversion of plastics into methane.

Climate change and energy policies, coal and coalmine methane in China

Energy Technology Data Exchange (ETDEWEB)

Ming Yang [3E& amp; T International, Beijing (China)

2009-08-15

The Chinese government has made many energy policies on coal, and coalmine methane (CMM) use. However, not all of these policies have effects or positive impacts. For example, it has been quite a few years since the national government made policies to encourage coalmine methane power to be sold to the grid. Practice showed that not one kilowatt of electricity was sold from a coalmine methane power plant to the grid in Sichuan and Guizhou Provinces as of December 2008. This paper reviews and evaluates the Chinese government energy and climate policies that are related to coal and coalmine methane, analyzes relevant policy barriers, and makes recommendations to overcome these barriers and avoid policy failures. The paper provides a literature review, challenges, resources, policies and other updated information on China's CMM recovery and utilization. The paper concludes that China needs to further reform its energy and environment management system, engage provincial governments in CMM capture and use activities, and provide incentives to qualified engineers and skilled workers to work in remote coal mining areas. This paper transfers key messages to policy makers for them to make better CMM capture and use policies. 15 refs., 3 figs., 3 tabs.

Climate change and energy policies, coal and coalmine methane in China

Energy Technology Data Exchange (ETDEWEB)

Yang, Ming [3E and T International, Suite 1506, Building No. 10, Luo Ma Shi Street, Xuanwu District, Beijing 100052 (China)

2009-08-15

The Chinese government has made many energy policies on coal, and coalmine methane (CMM) use. However, not all of these policies have effects or positive impacts. For example, it has been quite a few years since the national government made policies to encourage coalmine methane power to be sold to the grid. Practice showed that not any kilowatt of electricity was sold from a coalmine methane power plant to the grid in Sichuan and Guizhou Provinces as of December 2008. The objectives of this paper are to review and evaluate the Chinese government energy and climate policies that are related to coal and coalmine methane, analyze relevant policy barriers, and make recommendations to overcome these barriers and avoid policy failures. This paper provides the literature review, challenges, resources, policies and other updated information on China's CMM recovery and utilization. The paper concludes that China needs to further reform its energy and environment management system, engage provincial governments in CMM capture and use activities, and provide incentives to qualified engineers and skilled workers to work in remote coal mining areas. This paper transfers key messages to policy makers for them to make better CMM capture and use policies. (author)

Structural analysis of nickel doped cerium oxide catalysts for fuel reforming in solid oxide fuel cells

Science.gov (United States)

Cavendish, Rio

As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO 2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.

Methane airborne measurements and comparison to global models during BARCA

NARCIS (Netherlands)

Beck, Veronika; Chen, Huilin; Gerbig, Christoph; Bergamaschi, Peter; Bruhwiler, Lori; Houweling, Sander; Rockmann, Thomas; Kolle, Olaf; Steinbach, Julia; Koch, Thomas; Sapart, Celia J.; van der Veen, Carina; Frankenberg, Christian; Andreae, Meinrat O.; Artaxo, Paulo; Longo, Karla M.; Wofsy, Steven C.

2012-01-01

Tropical regions, especially the Amazon region, account for large emissions of methane (CH4). Here, we present CH4 observations from two airborne campaigns conducted within the BARCA (Balanco Atmosferico Regional de Carbono na Amazonia) project in the Amazon basin in November 2008 (end of the dry

Assessing the impact of rumen microbial communities on methane emissions and production traits in Holstein cows in a tropical climate.

Science.gov (United States)

Cunha, Camila S; Veloso, Cristina M; Marcondes, Marcos I; Mantovani, Hilario C; Tomich, Thierry R; Pereira, Luiz Gustavo R; Ferreira, Matheus F L; Dill-McFarland, Kimberly A; Suen, Garret

2017-12-01

The evaluation of how the gut microbiota affects both methane emissions and animal production is necessary in order to achieve methane mitigation without production losses. Toward this goal, the aim of this study was to correlate the rumen microbial communities (bacteria, archaea, and fungi) of high (HP), medium (MP), and low milk producing (LP), as well as dry (DC), Holstein dairy cows in an actual tropical production system with methane emissions and animal production traits. Overall, DC cows emitted more methane, followed by MP, HP and LP cows, although HP and LP cow emissions were similar. Using next-generation sequencing, it was found that bacteria affiliated with Christensenellaceae, Mogibacteriaceae, S24-7, Butyrivibrio, Schwartzia, and Treponema were negatively correlated with methane emissions and showed positive correlations with digestible dry matter intake (dDMI) and digestible organic matter intake (dOMI). Similar findings were observed for archaea in the genus Methanosphaera. The bacterial groups Coriobacteriaceae, RFP12, and Clostridium were negatively correlated with methane, but did not correlate with dDMI and dOMI. For anaerobic fungal communities, no significant correlations with methane or animal production traits were found. Based on these findings, it is suggested that manipulation of the abundances of these microbial taxa may be useful for modulating methane emissions without negatively affecting animal production. Copyright © 2017 Elsevier GmbH. All rights reserved.

Modeling, Simulation and Optimization of Hydrogen Production Process from Glycerol using Steam Reforming

International Nuclear Information System (INIS)

Park, Jeongpil; Cho, Sunghyun; Kim, Tae-Ok; Shin, Dongil; Lee, Seunghwan; Moon, Dong Ju

2014-01-01

For improved sustainability of the biorefinery industry, biorefinery-byproduct glycerol is being investigated as an alternate source for hydrogen production. This research designs and optimizes a hydrogen-production process for small hydrogen stations using steam reforming of purified glycerol as the main reaction, replacing existing processes relying on steam methane reforming. Modeling, simulation and optimization using a commercial process simulator are performed for the proposed hydrogen production process from glycerol. The mixture of glycerol and steam are used for making syngas in the reforming process. Then hydrogen are produced from carbon monoxide and steam through the water-gas shift reaction. Finally, hydrogen is separated from carbon dioxide using PSA. This study shows higher yield than former U.S.. DOE and Linde studies. Economic evaluations are performed for optimal planning of constructing domestic hydrogen energy infrastructure based on the proposed glycerol-based hydrogen station

Nitrate decreases ruminal methane production with slight changes to ruminal methanogen composition of nitrate-adapted steers.

Science.gov (United States)

Zhao, Liping; Meng, Qingxiang; Li, Yan; Wu, Hao; Huo, Yunlong; Zhang, Xinzhuang; Zhou, Zhenming

2018-03-20

This study was conducted to examine effects of nitrate on ruminal methane production, methanogen abundance, and composition. Six rumen-fistulated Limousin×Jinnan steers were fed diets supplemented with either 0% (0NR), 1% (1NR), or 2% (2NR) nitrate (dry matter basis) regimens in succession. Rumen fluid was taken after two-week adaptation for evaluation of in vitro methane production, methanogen abundance, and composition measurements. Results showed that nitrate significantly decreased in vitro ruminal methane production at 6 h, 12 h, and 24 h (P methane reduction was significantly related to Methanobrevibacter and Methanoplanus abundance, and negatively correlated with Methanosphaera and Methanimicrococcus abundance.

Evaluation and modeling of biochemical methane potential (BMP) of landfilled solid waste: a pilot scale study

DEFF Research Database (Denmark)

Bilgili, M Sinan; Demir, Ahmet; Varank, Gamze

2009-01-01

The main goal of this study was to present a comparison of landfill performance with respect to solids decomposition. Biochemical methane potential (BMP) test was used to determine the initial and the remaining CH(4) potentials of solid wastes during 27 months of landfilling operation in two pilot...... scale landfill reactors. The initial methane potential of solid wastes filled to the reactors was around 0.347 L/CH(4)/g dry waste, which decreased with operational time of landfill reactors to values of 0.117 and 0.154 L/CH(4)/g dry waste for leachate recirculated (R1) and non-recirculated (R2...

Methane Exchange in a Coastal Fen in the First Year after Flooding - A Systems Shift

Science.gov (United States)

Hahn, Juliane; Köhler, Stefan; Glatzel, Stephan; Jurasinski, Gerald

2015-01-01

Background Peatland restoration can have several objectives, for example re-establishing the natural habitat, supporting unique biodiversity attributes or re-initiating key biogeochemical processes, which can ultimately lead to a reduction in greenhouse gas (GHG) emissions. Every restoration measure, however, is itself a disturbance to the ecosystem. Methods Here, we examine an ecosystem shift in a coastal fen at the southern Baltic Sea which was rewetted by flooding. The analyses are based on one year of bi-weekly closed chamber measurements of methane fluxes gathered at spots located in different vegetation stands. During measurement campaigns, we recorded data on water levels, peat temperatures, and chemical properties of peat water. In addition we analyzed the first 20 cm of peat before and after flooding for dry bulk density (DBD), content of organic matter and total amounts of carbon (C), nitrogen (N), sulfur (S), and other nutrients. Results Rewetting turned the site from a summer dry fen into a shallow lake with water levels up to 0.60 m. We observed a substantial die-back of vegetation, especially in stands of sedges (Carex acutiformis Ehrh). Concentrations of total organic carbon and nitrogen in the peat water, as well as dry bulk density and concentrations of C, N and S in the peat increased. In the first year after rewetting, the average annual exchange of methane amounted to 0.26 ± 0.06 kg m-2. This is equivalent to a 190-times increase in methane compared to pre-flooding conditions. Highest methane fluxes occurred in sedge stands which suffered from the heaviest die-back. None of the recorded environmental variables showed consistent relationships with the amounts of methane exchanged. Conclusions Our results suggest that rewetting projects should be monitored not only with regard to vegetation development but also with respect to biogeochemical conditions. Further, high methane emissions that likely occur directly after rewetting by flooding should

Results from integral tests of single reformer tubes under simulated nuclear reactor conditions

International Nuclear Information System (INIS)

Decken, C.B. von der; Fedders, H.; Harth, R.; Hoehlein, B.; Riensche, E.

1980-01-01

The possibility of supplying high temperature heat from a HTGR for process application is being investigated at some places in the world. In all programmes or projects existing with respect to this application, the endothermic steam reforming of methane is one main step in the transmission of heat produced by nuclear fission to different chemical processes. The KFA is involved in the two German projects PNP - Prototypanlage Nukleare Prozesswaerme (Prototype-plant Nuclear Process-heat), and NFE -Nukleare Fernenergie (Long Distance Energy Transport). In a HTGR, helium generally serves as reactor coolant. It transports the heat from the core to the different components which take over this heat for various purposes. In case of arranging a steam reformer in the helium circuit, it is necessary for economic reasons to reach very high temperatures. In the two German projects mentioned above, the helium temperature at HTGR core outlet is determined to 950 0 C. Thus the main design data for a steam reformer supplied by heat from a HTGR are maximum helium temperature 950 0 C, helium pressure 40 bar. By an extensive utilization of the available advanced conventional steam reforming technology, the helium heated steam reformer design is using normal steam reforming tubes arranged in compact bundles

Reforming of Liquid Hydrocarbons in a Novel Hydrogen-Selective Membrane-Based Fuel Processor

Energy Technology Data Exchange (ETDEWEB)

Shamsuddin Ilias

2006-03-10

In this work, asymmetric dense Pd/porous stainless steel composite membranes were fabricated by depositing palladium on the outer surface of the tubular support. The electroless plating method combined with an osmotic pressure field was used to deposit the palladium film. Surface morphology and microstructure of the composite membranes were characterized by SEM and EDX. The SEM and EDX analyses revealed strong adhesion of the plated pure palladium film on the substrate and dense coalescence of the Pd film. Membranes were further characterized by conducting permeability experiments with pure hydrogen, nitrogen, and helium gases at temperatures from 325 to 450 C and transmembrane pressure differences from 5 to 45 psi. The permeation results showed that the fabricated membranes have both high hydrogen permeability and selectivity. For example, the hydrogen permeability for a composite membrane with a 20 {micro}m Pd film was 3.02 x 10{sup -5} moles/m{sup 2}.s.Pa{sup 0.765} at 450 C. Hydrogen/nitrogen selectivity for this composite membrane was 1000 at 450 C with a transmembrane pressure difference of 14.7 psi. Steam reforming of methane is one of the most important chemical processes in hydrogen and syngas production. To investigate the usefulness of palladium-based composite membranes in membrane-reactor configuration for simultaneous production and separation of hydrogen, steam reforming of methane by equilibrium shift was studied. The steam reforming of methane using a packed-bed inert membrane tubular reactor (PBIMTR) was simulated. A two-dimensional pseudo-homogeneous reactor model with parallel flow configuration was developed for steam reforming of methane. The shell volume was taken as the feed and sweep gas was fed to the inside of the membrane tube. Radial diffusion was taken into account for concentration gradient in the radial direction due to hydrogen permeation through the membrane. With appropriate reaction rate expressions, a set of partial differential

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)

Effect of unconventional oilseeds (safflower, poppy, hemp, camelina) on in vitro ruminal methane production and fermentation.

Science.gov (United States)

Wang, Shaopu; Kreuzer, Michael; Braun, Ueli; Schwarm, Angela

2017-08-01

Dietary supplementation with oilseeds can reduce methane emission in ruminants, but only a few common seeds have been tested so far. This study tested safflower (Carthamus tinctorius), poppy (Papaver somniferum), hemp (Cannabis sativa), and camelina (Camelina sativa) seeds in vitro using coconut (Cocos nucifera) oil and linseed (Linum usitatissimum) as positive controls. All the tested oilseeds suppressed methane yield (mL g -1 dry matter, up to 21%) compared to the non-supplemented control when provided at 70 g oil kg -1 dry matter, and they were as effective as coconut oil. Safflower and hemp were more effective than linseed (21% and 18% vs. 10%), whereas the effects of poppy and camelina were similar to linseed. When methane was related to digestible organic matter, only hemp and safflower seeds and coconut oil were effective compared to the non-supplemented control (up to 11%). The level of methanogenesis and the ratios of either the n-6:n-3 fatty acids or C 18 :2 :C 18 :3 in the seed lipids were not related. Unconventional oilseeds widen the spectrum of oilseeds that can be used in dietary methane mitigation. In vivo confirmation of their methane mitigating effect is still needed, and their effects on animal performance still must be determined. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Effect of technical cashew nut shell liquid on rumen methane emission and lactation performance of dairy cows.

Science.gov (United States)

Branco, A F; Giallongo, F; Frederick, T; Weeks, H; Oh, J; Hristov, A N

2015-06-01

Technical-grade cashew nut shell liquid (TCNSL) is a by-product of the cashew nut industry in tropical countries, and is known to exhibit a wide range of biological activities, including inhibitory effect against gram-positive bacteria. This study was conducted to investigate the effects of TCNSL (73.3% cardanol, 16.4% cardol, and 3.0% methylcardol) on rumen methane emission, nutrient digestibility, dry matter intake, and milk yield and composition in dairy cows. Eight multiparous Holstein cows were used in a crossover design trial with two 21-d experimental periods. The diet was based on corn silage and alfalfa haylage and was formulated to meet or exceed the energy and metabolizable protein requirements of the cows. Treatments were control (no TCNSL supplementation) or 30 g/cow per day of TCNSL. Rumen carbon dioxide emission was not affected by TCNSL. Treatment had no effect on methane emission (542 vs. 511±35.3 g/cow per day, respectively) and methane emission intensity (15.0 vs. 13.9±0.58 g/kg of energy-corrected milk, respectively) and tended to decrease methane emission per kilogram of dry matter intake (20.2 vs. 18.6±1.04 g/kg, respectively). Dry matter intake (average 26.9±1.00 kg/d), milk yield (40.0±1.73 kg/d), and milk composition were not different between treatments. The TCNSL had no effect on N losses in urine and feces and total-tract apparent digestibility of nutrients, except digestibility of neutral detergent fiber tended to be increased compared with the control. Plasma urea and glucose concentrations were not affected by TCNSL. Concentration of milk C18:0 tended to be decreased (17%) by TCNSL compared with the control. In this study, TCNSL did not alter absolute methane emission in the rumen, but tended to decrease it by 8% per kilogram of dry matter intake. The TCNSL had no effect on milk yield and composition in dairy cows. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

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.

MERLIN: A French-German Space Lidar Mission Dedicated to Atmospheric Methane

Directory of Open Access Journals (Sweden)

Gerhard Ehret

2017-10-01

Full Text Available The MEthane Remote sensing Lidar missioN (MERLIN aims at demonstrating the spaceborne active measurement of atmospheric methane, a potent greenhouse gas, based on an Integrated Path Differential Absorption (IPDA nadir-viewing LIght Detecting and Ranging (Lidar instrument. MERLIN is a joint French and German space mission, with a launch currently scheduled for the timeframe 2021/22. The German Space Agency (DLR is responsible for the payload, while the platform (MYRIADE Evolutions product line is developed by the French Space Agency (CNES. The main scientific objective of MERLIN is the delivery of weighted atmospheric columns of methane dry-air mole fractions for all latitudes throughout the year with systematic errors small enough (<3.7 ppb to significantly improve our knowledge of methane sources from global to regional scales, with emphasis on poorly accessible regions in the tropics and at high latitudes. This paper presents the MERLIN objectives, describes the methodology and the main characteristics of the payload and of the platform, and proposes a first assessment of the error budget and its translation into expected uncertainty reduction of methane surface emissions.

Methane airborne measurements and comparison to global models during BARCA

NARCIS (Netherlands)

Beck, V.; Chen, H.; Gerbig, C; Bergamaschi, P.; Bruhwiler, L.; Houweling, S.; Röckmann, T.; Kolle, O.; Steinbach, J.; Koch, T.; Sapart, C.J.; van der Veen, C.; Frankenberg, C.; Andreae, M.O.; Artaxo, P.; Longo, K.M.; Wofsy, S.C.

2012-01-01

Tropical regions, especially the Amazon region, account for large emissions of methane (CH4). Here, we present CH4 observations from two airborne campaigns conducted within the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) project in the Amazon basin in November 2008 (end of the dry

Thermodynamic analysis of carbon formation in solid oxide fuel cells with a direct internal reformer fueled by ethanol, methanol, and methane

International Nuclear Information System (INIS)

Laosiripojana, N.; Assabumrungrat, S.; Pavarajarn, V.; Sangtongkitcharoen, W.; Tangjitmatee, A.; Praserthdam, P.

2004-01-01

'Full text:' This paper concerns a detailed thermodynamic analysis of carbon formation for a Direct Internal Reformer (DIR) Solid Oxide Fuel Cells (SOFC). The modeling of DIR-SOFC fueled by ethanol, methanol, and methane were compared. Two types of fuel cell electrolytes, i.e. oxygen-conducting and hydrogen-conducting, are considered. Equilibrium calculations were performed to find the ranges of inlet steam/fuel ratio where carbon formation is thermodynamically unfavorable in the temperature range of 500-1200 K. It was found that the key parameters determining the boundary of carbon formation are temperature, type of solid electrolyte and extent of the electrochemical reaction of hydrogen. The minimum requirements of H2O/fuel ratio for each type of fuel in which the carbon formation is thermodynamically unfavored were compared. At the same operating conditions, DIR-SOFC fueled by ethanol required the lowest inlet H2O/fuel ratio in which the carbon formation is thermodynamically unfavored. The requirement decreased with increasing temperature for all three fuels. Comparison between two types of the electrolytes reveals that the hydrogen-conducting electrolyte is impractical for use, regarding to the tendency of carbon formation. This is due mainly to the water formed by the electrochemical reaction at the electrodes. (author)

CO 2-scrubbing and methanation as purification system for PEFC

Science.gov (United States)

Ledjeff-Hey, K.; Roes, J.; Wolters, R.

Hydrogen is usually produced by steam reforming of natural gas in large-scale processes. The reformate consists of hydrogen, carbon dioxide, carbon monoxide, and residues of hydrocarbons. Since the anode catalyst of a polymer electrolyte membrane fuel cell (PEFC) is usually based on platinum, which is easily poisoned by carbon monoxide, the conditioned feed gas should contain less than 100 ppmv CO, and preferably, less than 10 ppmv. Depending on the design and operating conditions of the hydrogen production process, the CO content of a typical reformate gas, even after the CO shift reactor may be in the range of 0.2-1.0 vol.%; this is far higher than a PEFC can tolerate. A CO management system is required to lower the CO concentration to acceptable levels. In many cases, the CO purification system consists of a combination of physical or chemical processes to achieve the necessary reduction in CO content. A promising alternative for hydrogen purification is a combined process consisting of a carbon dioxide scrubber with subsequent methanation to reduce the carbon monoxide content to an acceptable level of less than 10 ppmv.

Hydrocarbon reforming catalysts and new reactor designs for compact hydrogen generators

Energy Technology Data Exchange (ETDEWEB)

Schaefer, A.; Schwab, E.; Urtel, H. [BASF SE, Ludwigshafen (Germany); Farrauto, R. [BASF Catalysts LLC, Iselin, NJ (United States)

2010-12-30

A hydrogen based future energy scenario will use fuel cells for the conversion of chemically stored energy into electricity. Depending upon the type of fuel cell, different specifications will apply for the feedstock which is converted in the cell, ranging from very clean hydrogen for PEM-FC's to desulfurized methane for SOFC and MCFC technology. For the foreseeable future, hydrogen will be supplied by conventional reforming, however operated in compact and dynamic reformer designs. This requires that known catalyst formulations are offered in specific geometries, giving flexibility for novel reactor design options. These specific geometries can be special tablet shapes as well as monolith structures. Finally, also nonhydrocarbon feedstock might be used in special applications, e.g. bio-based methanol and ethanol. BASF offers catalysts for the full process chain starting from feedstock desulfurization via reforming, high temperature shift, low temperature shift to CO fine polishing either via selective oxidation or selective methanation. Depending upon the customer's design, most stages can be served either with precious metal based monolith solutions or base metal tablet solutions. For the former, we have taken the automobile catalyst monolith support and extended its application to the fuel cell hydrogen generation. Washcoats of precious metal supported catalysts can for example be deposited on ceramic monoliths and/or metal heat exchangers for efficient generation of hydrogen. Major advantages are high through puts due to more efficient heat transfer for catalysts on metal heat exchangers, lower pressure drop with greater catalyst mechanical and thermal stability compared to particulate catalysts. Base metal tablet catalysts on the other hand can have intrinsic cost advantages, larger fractions of the reactor can be filled with active mass, and if produced in unconventional shape, again novel reactor designs are made possible. Finally, if it comes to

Energy efficient selective reforming of hydrocarbons. ERA-NET Bioenergy. Final report

Energy Technology Data Exchange (ETDEWEB)

Rodin, J.

2010-07-15

The research project 'Energy efficient selective reforming of hydrocarbons', funded by the Swedish and Energinet.dk Agency has now reached its end. The report is an overview of the work. Details of the work within the different areas can be found in the reports from each part. In this project, an innovative method for tar removal and reformation of hydrocarbons was investigated: Chemical Looping Reforming (CLR). This gas treatment has the potential to be economically competitive, reliable and environmentally friendly (due to higher energy efficiency, amongst others). The aim of the CLR is to 1) eliminate downstream problems with tar 2) simplify the energy recovery from the hot product gas 3) selectively save lighter hydrocarbons for the production of synthetic natural gas (SNG). A guarantor for the outcome of the project is the engagement of Goeteborg Energi, which has a commitment to build a 20 MW output SNG plant by 2012. DTU (Danish Technical University) is responsible for carrying out the laboratorial part, where different oxygen carriers for the CLR have been considering their capability of selectively reforming hydrocarbons. The conclusion was that, of the four carriers tested, the Mn and Ni40 was the most promising. CUT (Chalmers University of Technology) has installed a 600 W CLR unit connected to a slipstream from the gasifier. During the firing season 2010 the CLR has been tested with raw gas for 36 hours and the results so far show that the equipment works as intended and that it can reduce the amount of tars substantially. GE (Goeteborg Energi AB) together with SEP (Scandinavian Energy Project AB) and CUT have studied the integration of a methane production plant to an existing boiler. The main focus of the study has been the gasifier and the CLR. The integration of a 100 MW methane production plant is estimated to cost 1.3-2.4 billion SEK. The different work packages have altogether shown that a CLR is a possible solution to the tar problem

Effects of water vapor on the radiolysis of methane over molecular sieve 5A

International Nuclear Information System (INIS)

Shimizu, Y.; Nagai, S.

1989-01-01

Effects of the addition of H 2 O on the radiation-induced chemical reaction of methane over molecular sieve 5A at 460 0 C have been studied by product analysis. Hydrogen, carbon monoxide, carbon dioxide and hydrocarbons consisting mainly of C 2 and C 3 alkanes and alkenes were produced from CH 4 + H 2 O mixtures at high conversion levels. The yields of hydrocarbons from 3:1 and 3:2 CH 4 + H 2 O mixtures decreased slightly with time but those from 3:4 mixture showed no decrease with time. When the molecular sieve 5A that had been irradiated in flowing methane was reirradiated in the presence of H 2 O, carbonaceous solid produced from methane on molecular sieve 5A was readily decomposed to carbon dioxide, carbon monoxide, hydrogen and hydrocarbons, mainly alkanes. Therefore, it is concluded that the suppression of decrease of product yields with time by the addition of H 2 O is mainly ascribed to decomposition of the carbonaceous solid by H 2 O under electron beam irradiation. The role of added H 2 O is also discussed in connection with the conventional methane-steam reforming reaction. (author)

Pre elementary design of primary reformer for hydrogen plant coupled with HTGR type NPP

International Nuclear Information System (INIS)

Dedy Priambodo; Erlan Dewita; Sudi Ariyanto

2012-01-01

Hydrogen has a high potent for new energy, because of it availability. Steam reforming is a fully developed commercial technology and is the most economical method for production of hydrogen. Steam reforming uses an external source of hot gas to heat tubes in which a catalytic reaction takes place that converts steam and lighter hydrocarbons such as natural gas (methane) or refinery feedstock into hydrogen and carbon monoxide (syngas) at high temperature on primary reformer (800-900°C). Utilization of helium from HTGR as heating medium for primary reformer has consequence to type and shape of its reactor. The main goal of this paper is to determine type/shape and pre elementary design of chemical reactor for the cogeneration system of Hydrogen Plant and HTGR The primary reformer for this system is Fixed Bed Multitube reactor with specification tube: NPS 3,5 Sch 40 ST 40S, 0.281 in thickness, number of tube 849 pieces and ASTM HH 30 for tube material. Tube arrangement is 'triangular pitch' on shell Split-Ring Floating Head from Steel Alloy SA 301 Grade B equipted with 8 baffles. (author)

In vitro evaluation of different varieties of maize fodder for their methane generation potential and digestibility with goat rumen liquor.

Science.gov (United States)

Vaswani, Shalini; Kumar, Ravindra; Kumar, Vinod; Roy, Debashis; Kumar, Muneendra

2016-11-01

To evaluate the methane generation potential and digestibility of different (normal and three high-quality protein maize [HQPM]) varieties of maize fodder with goat rumen liquor in vitro . Methane production potential and digestibility of different varieties of maize fodder were tested in in vitro gas production test. Seven varieties of maize, four normal (HTHM 5101, DHM 117, HM 5, and Shaktiman/900 M Gold), and three high-quality protein (HQPM 5, HQPM 7, and HQPM 9/Vivek) were grown in different plots under the same environmental and agro-climatic conditions. Fodders were harvested at 45-50 days of sowing, and the representative samples of fodder from different varieties of maize were collected for analysis. Dried and grinded form of these maize fodder varieties was tested for gas, methane, and digestibility using goat rumen microflora in in vitro gas syringes. Gas production (ml/g dry matter [DM]) was highest for HM5 variety (97.66, whereas lowest for HQPM 9 variety (64.22). Gas production (ml/g degraded DM [DDM]) and methane (%) were statistically similar in different varieties of maize fodder. The methane production expressed as ml/g DM and ml/g DDM was significantly (pproduction.

Development and characterization of nickel catalysts supported in CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} matrixes evaluated for methane reforming reactions; Desenvolvimento e caracterização de catalisadores de níquel suportados em matrizes CeO{sub 2}-ZrO{sub 2}-Al{sub 2}O{sub 3}, CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} e ZrO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3} avaliados para as reações de reforma do metano

Energy Technology Data Exchange (ETDEWEB)

Abreu, Amanda Jordão de

2012-07-01

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{sub 2}O{sub 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{sub 2}O{sub 3} supported on solid solutions formed by ZrO{sub 2}-CeO{sub 2}, La{sub 2}O{sub 3} and CeO{sub 2}-ZrO{sub 2}-La{sub 2}O{sub 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{sub 2}O{sub 3} catalysts and the best catalysts are Ni/CeO{sub 2}-La{sub 2}O{sub 3}-Al{sub 2}O{sub 3}. (author)

Combined steam and carbon dioxide reforming of methane and side reactions: Thermodynamic equilibrium analysis and experimental application

International Nuclear Information System (INIS)

Jang, Won-Jun; Jeong, Dae-Woon; Shim, Jae-Oh; Kim, Hak-Min; Roh, Hyun-Seog; Son, In Hyuk; Lee, Seung Jae

2016-01-01

Highlights: • Selected variables have a significant influence on yields of synthesis gas. • (CO_2 + H_2O)/CH_4 affects the temperature which can achieve the maximum conversion. • Coke is formed at low temperatures even with excess oxidizing agent. • The occurrence of RWGS becomes critical in real chemical reactions. • Equilibrium conversions are maintained for 500 h without detectable deactivation. - Abstract: Thermodynamic equilibrium analysis of the combined steam and carbon dioxide reforming of methane (CSCRM) and side reactions was performed using total Gibbs free energy minimization. The effects of (CO_2 + H_2O)/CH_4 ratio (0.9–2.9), CO_2:H_2O ratio (3:1–1:3), and temperature (500–1000 °C) on the equilibrium conversions, yields, coke yield, and H_2/CO ratio were investigated. A (CO_2 + H_2O)/CH_4 ratio greater than 1.2, a CO_2:H_2O ratio of 1:2.1, and a temperature of at least 850 °C are preferable reaction conditions for the synthesis gas preparation in the gas to liquid process. Simulated conditions were applied to the CSCRM reaction and the experimental data were compared with the thermodynamic equilibrium results. The thermodynamic equilibrium results were mostly consistent with the experimental data, but the reverse water gas shift reaction rapidly occurred in the real chemical reaction and under excess oxidizing agent conditions. In addition, a long-term stability test (under simulated conditions) showed that the equilibrium conversion was maintained for 500 h and that the coke formation on the used catalyst was not observed.

Study on methane separation from steam reforming product gas with polyimide membrane

International Nuclear Information System (INIS)

Koiso, Hiroshi; Inagaki, Yoshiyuki; Aita, Hideki; Sekita, Kenji; Haga, Katsuhiro; Hino, Ryutaro.

1997-10-01

In the HTTR hydrogen production system by steam reforming of natural gas (main component: CH 4 ), CH 4 conversion rate is limited to approximately 65% due to high pressure and low temperature conditions (4.5 MPa, 800degC). The one of the measures to improve CH 4 conversion is recycling of residual CH 4 extracted from steam reforming product gas with a gas separator. Experimental and analytical studies on CH 4 separation from gas mixture composed of CH 4 , H 2 , CO 2 and CO were carried out to investigate gas separation characteristics of a polyimide membrane gas separator. Measured permeability of each gas in gas mixture was reduced from 1/3 to 1/14 of that obtained with a single gas (catalog value). The polyimide membrane could extracted CH 4 of approximately 80% from gas mixture, then, H 2 and CO 2 more than 98% were removed. It was confirmed that the polyimide membrane could be available to residual CH 4 recycling. The analytical results by a difference method gave good prospects of experimental results such as permeated flow rate, mol-fraction profiles and so on. Therefore, it can be said the analysis method was established. (author)

Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

KAUST Repository

Zhang, Xuming

2015-01-01

We studied the relative importance of the reduced field intensity and the background reaction temperature in the partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor. We obtained important mechanistic insight from studying high-temperature and low-pressure conditions with similar reduced field intensities. In the tested range of background temperatures (297 < T < 773 K), we found that the conversion of methane and oxygen depended on both the electron-induced chemistry and the thermo-chemistry, whereas the chemical pathways to the products were overall controlled by the thermo-chemistry at a given temperature. We also found that the thermo-chemistry enhanced the plasma-assisted partial oxidation process. Our findings expand our understanding of the plasma-assisted partial oxidation process and may be helpful in the design of cost-effective plasma reformers. © 2014 The Combustion Institute.

Grafted NiO on natural olivine for dry reforming of methane

Directory of Open Access Journals (Sweden)

Grafted NiO on natural olivine for dry reforming of methane C Courson, L Udron, C Petit and A Kiennemann Sci. Technol. Adv. Mater. 3 No 3 (June 2002 271-282 Abstract | References Full text: Acrobat PDF (1.10 MB

2002-01-01

Full Text Available Natural olivine is used for gasification of biomass in a fluidised bed. Characterisations by X-ray diffraction and electron microscopies (SEM and TEM have proved the presence of a (Mg,Fe2SiO4 structure (Mg/Fe ratio: 9/1 with a rather broad distribution in elemental composition. Temperature programmed reduction has revealed equally the presence of iron oxides outside of this structure. The nature of free iron oxides can be both modified by increasing the temperature of calcination and confirmed by measurements of magnetism.The introduction of nickel oxide upon natural olivine is obtained by impregnation with a nitrate salt. The type of interaction of nickel oxide with olivine is different depending upon the preparation method and the calcination temperature. For calcination at 1100 °C, the effects of the amount of NiO and the number of impregnation have been studied. At a high temperature of calcination (1400 °C, NiO is integrated into the olivine structure and the amount of free iron increases. Integrated NiO on olivine is non-reducible, resulting in an inactive catalyst. At lower calcination temperatures grafted NiO is formed, a species which is reduced under catalytic test conditions without aggregation of particles. A single impregnation of nickel (5.5 wt% of NiO gives a stable catalyst activated directly under reaction conditions (CH4+CO2 yielding 96% CO and 76% H2. Catalysts with lower amounts of NiO or a double impregnation of nickel salt lead to a less stable system.Analysis reveals that no change in olivine structure nor size of nickel deposit occurs under test conditions. Equally there are no carbon deposits formed on these catalysts. A model of the evolution of each catalytic system arising from the different preparation methods is proposed. The observed deactivation of such catalysts is attributed to the increase in the amount of free iron, which favours the oxidative properties of the catalytic system.

Development, investigation and modelling of a micro reformer as part of a system for off-grid power supply with PEM fuel cells

Energy Technology Data Exchange (ETDEWEB)

Rochlitz, Lisbeth

2008-11-18

In this thesis a micro reformer fuel cell system ({mu}RFCS) for 300 Wel off-grid power supply, fuelled with bioethanol, was simulated, designed, developed and investigated in a test-rig. First a literature study was carried through to point out the specific characteristics of micro reforming, the most important being heat transfer, and present the systems currently under research and already on the market. As a next step, the processes of the RFCS were simulated with the commercial simulation tool CHEMCAD. This comprised thermodynamic equilibrium simulations for the separate reactions of steam reforming, water gas shift and selective methanation. It also included a simulation of the complete {mu}RFCS with thermodynamic equilibrium for all reactors and assumed values for heat loss and fuel cell efficiency. The resulting net electrical efficiency was 24%. As a third step, a reaction pathway scheme with parallel and serial reactions for the steam reforming reaction of ethanol was simulated, developed, evaluated and proven plausible by matching the simulation to experimental results obtained in the {mu}RFCS test rig. The equilibrium simulations were used to evaluate the catalyst screening carried through for reformer, water gas shift and selective methanation catalysts. The catalysts for the {mu}RFCS were chosen and the optimum operating conditions determined by the screening tests. Having accomplished the simulation and design of the system, the largest proportion of this work was spent on the construction, set-up, testing and evaluation of the complete {mu}RFCS. The focus for the evaluations lay on the reformer side of the system. The technical feasibility was demonstrated for an ethanol/water mix of 3 ml/min at S/C 3. The first tests without optimized heat and water management between the reformer system and the fuel cell system resulted in power output of around 115 W{sub el}, at a total electrical efficiency of 31%. (orig.)

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.

EVALUATING HYDROGEN PRODUCTION IN BIOGAS REFORMING IN A MEMBRANE REACTOR

Directory of Open Access Journals (Sweden)

F. S. A. Silva

2015-03-01

Full Text Available Abstract Syngas and hydrogen production by methane reforming of a biogas (CH4/CO2 = 2.85 using carbon dioxide was evaluated in a fixed bed reactor with a Pd-Ag membrane in the presence of a nickel catalyst (Ni 3.31% weight/γ-Al2O3 at 773 K, 823 K, and 873 K and 1.01×105 Pa. Operation with hydrogen permeation at 873 K increased the methane conversion to approximately 83% and doubled the hydrogen yield relative to operation without hydrogen permeation. A mathematical model was formulated to predict the evolution of the effluent concentrations. Predictions based on the model showed similar evolutions for yields of hydrogen and carbon monoxide at temperatures below 823 K for operations with and without the hydrogen permeation. The hydrogen yield reached approximately 21% at 823 K and 47% at 873 K under hydrogen permeation conditions.

Research on estimation of methane generated in paddy field and release mechanism of the gas into the atmosphere. Suiden ni okeru methane hasseiryo no hyoka to sono hoshutsu kiko ni kansuru kenkyu

Energy Technology Data Exchange (ETDEWEB)

Minami, K; Nouchi, I; Yagi, K [National Institute of Agro-Environmental Science, Tsukuba (Japan)

1991-11-25

Research and estimation have been carried out on a mechanism to generate methane in paddy fields, which relates closely to global warming. For methane flux measurement, the chamber method was used. The result revealed that with paddy fields mixed with organic substances, methane generation was abundant in the order of raw rice straw mixed area > rice straw compost mixed area > chemical fertilizer mixed area. At the Ryugasaki test area, the raw rice straw and fertilizer mixed areas have generated methane annually at 27.0 gm[sup [minus]2] and 8.2 gm[sup [minus]2], respectively. With regard to soil types, the order was peat soil > gley soil > Kuroboku soil > light-colored Kuroboku soil, where the peat soil generated about 40 times as much of methane as the light-colored Kuroboku soil. As regards the influence from drainage adjustment, normally water-filled field, wet field, and dry field generated methane at 9.25, 4.79, and 0.34 gm[sup [minus]1] y[sup [minus]1], respectively. Amount of methane generated annually from paddy fields over the whole world was estimated at 22 to 73[times]10[sup 12] g. It was determined from the above facts that methane generation may be reduced if organic substance mixing and water in paddy fields are controlled properly. 8 refs., 5 figs., 1 tab.

Thermodynamic analysis of a membrane-assisted chemical looping reforming reactor concept for combined H2 production and CO2 capture

NARCIS (Netherlands)

Medrano Jimenez, J.A.; Spallina, V.; Sint Annaland, van M.; Gallucci, F.

2014-01-01

There is great consensus that hydrogen will become an important energy carrier in the future. Currently, hydrogen is mainly produced by steam reforming of natural gas/methane on large industrial scale or by electrolysis of water when high-purity hydrogen is needed for small-scale hydrogen plants.

Role of Age-Related Shifts in Rumen Bacteria and Methanogens in Methane Production in Cattle

Directory of Open Access Journals (Sweden)

Chong Liu

2017-08-01

Full Text Available Rumen microbiota are essential for maintaining digestive and metabolic functions, producing methane as a byproduct. Dairy heifers produce large amounts of methane based on fermentation of digested organic matter, with adverse consequences for feed efficiency and the environment. It is therefore important to understand the influence of host age on the relationship between microbiota and methane production. This study explored the age effect on the relationship between microbial communities and enteric methane production in dairy cows and heifers using high-throughput sequencing. Methane production and volatile fatty acid concentrations were age-related. Heifers (9–10 months had lower methane production but higher methane production per dry matter intake (DMI. The acetate:propionate ratio decreased significantly with increasing age. Age-related microbiota changes in the rumen were reflected by a significant shift in bacterial taxa, but relatively stable archaeal taxa. Prevotella, Ruminococcus, Flavonifractor, Succinivibrio, and Methanobrevibacter were affected by age. This study revealed different associations between predominant bacterial phylotypes and Methanobrevibacter with increasing age. Prevotella was strongly correlated with Methanobrevibacter in heifers; howerver, in older cows (96–120 months this association was replaced by a correlation between Succinivibrio and Methanobrevibacter. This shift may account for the age-related difference in rumen fermentation and methane production per DMI.

Methane bursts as a trigger for intermittent lake-forming climates on post-Noachian Mars

Science.gov (United States)

Kite, Edwin S.; Gao, Peter; Goldblatt, Colin; Mischna, Michael A.; Mayer, David P.; Yung, Yuk L.

2017-10-01

Lakes existed on Mars later than 3.6 billion years ago, according to sedimentary evidence for deltaic deposition. The observed fluviolacustrine deposits suggest that individual lake-forming climates persisted for at least several thousand years (assuming dilute flow). But the lake watersheds’ little-weathered soils indicate a largely dry climate history, with intermittent runoff events. Here we show that these observational constraints, although inconsistent with many previously proposed triggers for lake-forming climates, are consistent with a methane burst scenario. In this scenario, chaotic transitions in mean obliquity drive latitudinal shifts in temperature and ice loading that destabilize methane clathrate. Using numerical simulations, we find that outgassed methane can build up to atmospheric levels sufficient for lake-forming climates, if methane clathrate initially occupies more than 4% of the total volume in which it is thermodynamically stable. Such occupancy fractions are consistent with methane production by water-rock reactions due to hydrothermal circulation on early Mars. We further estimate that photochemical destruction of atmospheric methane curtails the duration of individual lake-forming climates to less than a million years, consistent with observations. We conclude that methane bursts represent a potential pathway for intermittent excursions to a warm, wet climate state on early Mars.

System design study of a membrane reforming hydrogen production plant using a small sized sodium cooled reactor

International Nuclear Information System (INIS)

Chikazawa, Y.; Konomura, M.; Hori, T.; Sato, H.; Uchida, S.

2004-01-01

In this study, a membrane reforming hydrogen production plant using a small sized sodium cooled reactor was designed as one of promising concepts. In the membrane reformer, methane and steam are reformed into carbon dioxide and hydrogen with sodium heat at a temperature 500 deg-C. In the equilibrium condition, steam reforming proceeds with catalyst at a temperature more than 800 deg-C. Using membrane reformers, the steam reforming temperature can be decreased from 800 to 500 deg-C because the hydrogen separation membrane removes hydrogen selectively from catalyst area and the partial pressure of hydrogen is kept much lower than equilibrium condition. In this study, a hydrogen and electric co-production plant has been designed. The reactor thermal output is 375 MW and 25% of the thermal output is used for hydrogen production (70000 Nm 3 /h). The hydrogen production cost is estimated to 21 yen/Nm 3 but it is still higher than the economical goal (17 yen/Nm 3 ). The major reason of the high cost comes from the large size of hydrogen separation reformers because of the limit of hydrogen separation efficiency of palladium membrane. A new highly efficient hydrogen separation membrane is needed to reduce the cost of hydrogen production using membrane reformers. There is possibility of multi-tube failure in the membrane reformers. In future study, a design of measures against tube failure and elemental experiments of reaction between sodium and reforming gas will be needed. (authors)

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...... different surface areas (ranging from 20 to 235 m2 g-1) in this reaction. The activity for CO methanation, under steady-state conditions, was found to strongly depend on the TiO2 support surface area, increasing first with increasing surface area up to a maximum activity for the Ru/TiO2 catalyst...... with a surface area of 121 m2 g-1 and then decreasing for an even higher surface area; however, the selectivity is mainly determined by the Ru particle size, which slightly decreases with increasing support surface area. This goes along with an increase in selectivity for CO methanation, in agreement...

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.

Characterization of Methane Degradation and Methane-Degrading Microbes in Alaska Coastal Water

Energy Technology Data Exchange (ETDEWEB)

Kirchman, David L. [Univ. of Delaware, Lewes, DE (United States)

2012-03-29

The net flux of methane from methane hydrates and other sources to the atmosphere depends on methane degradation as well as methane production and release from geological sources. The goal of this project was to examine methane-degrading archaea and organic carbon oxidizing bacteria in methane-rich and methane-poor sediments of the Beaufort Sea, Alaska. The Beaufort Sea system was sampled as part of a multi-disciplinary expedition (Methane in the Arctic Shelf or MIDAS) in September 2009. Microbial communities were examined by quantitative PCR analyses of 16S rRNA genes and key methane degradation genes (pmoA and mcrA involved in aerobic and anaerobic methane degradation, respectively), tag pyrosequencing of 16S rRNA genes to determine the taxonomic make up of microbes in these sediments, and sequencing of all microbial genes (metagenomes ). The taxonomic and functional make-up of the microbial communities varied with methane concentrations, with some data suggesting higher abundances of potential methane-oxidizing archaea in methane-rich sediments. Sequence analysis of PCR amplicons revealed that most of the mcrA genes were from the ANME-2 group of methane oxidizers. According to metagenomic data, genes involved in methane degradation and other degradation pathways changed with sediment depth along with sulfate and methane concentrations. Most importantly, sulfate reduction genes decreased with depth while the anaerobic methane degradation gene (mcrA) increased along with methane concentrations. The number of potential methane degradation genes (mcrA) was low and inconsistent with other data indicating the large impact of methane on these sediments. The data can be reconciled if a small number of potential methane-oxidizing archaea mediates a large flux of carbon in these sediments. Our study is the first to report metagenomic data from sediments dominated by ANME-2 archaea and is one of the few to examine the entire microbial assemblage potentially involved in

Thermodynamic evaluation of hydrogen production via bioethanol steam reforming

Energy Technology Data Exchange (ETDEWEB)

Tasnadi-Asztalos, Zsolt; Cormos, Ana-Maria; Imre-Lucaci, Árpád; Cormos, Călin C. [Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, Arany Janos 11, RO-400028, Cluj-Napoca (Romania)

2013-11-13

In this article, a thermodynamic analysis for bioethanol steam reforming for hydrogen production is presented. Bioethanol is a newly proposed renewable energy carrier mainly produced from biomass fermentation. Reforming of bioethanol provides a promising method for hydrogen production from renewable resources. Steam reforming of ethanol (SRE) takes place under the action of a metal catalyst capable of breaking C-C bonds into smaller molecules. A large domain for the water/bioethanol molar ratio as well as the temperature and average pressure has been used in the present work. The interval of investigated temperature was 100-800°C, the pressure was in the range of 1-10 bar and the molar ratio was between 3-25. The variations of gaseous species concentration e.g. H{sub 2}, CO, CO{sub 2}, CH{sub 4} were analyzed. The concentrations of the main products (H{sub 2} and CO) at lower temperature are smaller than the ones at higher temperature due to by-products formation (methane, carbon dioxide, acetylene etc.). The concentration of H2 obtained in the process using high molar ratio (>20) is higher than the one at small molar ratio (near stoichiometric). When the pressure is increased the hydrogen concentration decreases. The results were compared with literature data for validation purposes.

Non-catalytic plasma-arc reforming of natural gas with carbon dioxide as the oxidizing agent for the production of synthesis gas or hydrogen

OpenAIRE

Blom, P.W.E.; Basson, G.W.

2013-01-01

The world’s energy consumption is increasing constantly due to the growing population of the world. The increasing energy consumption has a negative effect on the fossil fuel reserves of the world. Hydrogen has the potential to provide energy for all our needs by making use of fossil fuel such as natural gas and nuclear-based electricity. Hydrogen can be produced by reforming methane with carbon dioxide as the oxidizing agent. Hydrogen can be produced in a Plasma-arc reforming ...

Chemical Looping Combustion of Hematite Ore with Methane and Steam in a Fluidized Bed Reactor

Directory of Open Access Journals (Sweden)

Samuel Bayham

2017-08-01

Full Text Available Chemical looping combustion is considered an indirect method of oxidizing a carbonaceous fuel, utilizing a metal oxide oxygen carrier to provide oxygen to the fuel. The advantage is the significantly reduced energy penalty for separating out the CO2 for reuse or sequestration in a carbon-constrained world. One of the major issues with chemical looping combustion is the cost of the oxygen carrier. Hematite ore is a proposed oxygen carrier due to its high strength and resistance to mechanical attrition, but its reactivity is rather poor compared to tailored oxygen carriers. This problem is further exacerbated by methane cracking, the subsequent deposition of carbon and the inability to transfer oxygen at a sufficient rate from the core of the particle to the surface for fuel conversion to CO2. Oxygen needs to be readily available at the surface to prevent methane cracking. The purpose of this work was to demonstrate the use of steam to overcome this issue and improve the conversion of the natural gas to CO2, as well as to provide data for computational fluid dynamics (CFD validation. The steam will gasify the deposited carbon to promote the methane conversion. This work studies the performance of hematite ore with methane and steam mixtures in a 5 cm fluidized bed up to approximately 140 kPa. Results show an increased conversion of methane in the presence of steam (from 20–45% without steam to 60–95% up to a certain point, where performance decreases. Adding steam allows the methane conversion to carbon dioxide to be similar to the overall methane conversion; it also helped to prevent carbon accumulation from occurring on the particle. In general, the addition of steam to the feed gas increased the methane conversion. Furthermore, the addition of steam caused the steam methane reforming reaction to form more hydrogen and carbon monoxide at higher steam and methane concentrations, which was not completely converted at higher concentrations and

Techno-economic analysis of sorption-enhanced steam methane reforming in a fixed bed reactor network integrated with fuel cell

Science.gov (United States)

Diglio, Giuseppe; Hanak, Dawid P.; Bareschino, Piero; Mancusi, Erasmo; Pepe, Francesco; Montagnaro, Fabio; Manovic, Vasilije

2017-10-01

Sorption-enhanced steam methane reforming (SE-SMR) is a promising alternative for H2 production with inherent CO2 capture. This study evaluates the techno-economic performance of SE-SMR in a network of fixed beds and its integration with a solid oxide fuel cell (SE-SMR-SOFC) for power generation. The analysis revealed that both proposed systems are characterised by better economic performance than the reference systems. In particular, for SE-SMR the levelised cost of hydrogen is 1.6 €ṡkg-1 and the cost of CO2 avoided is 29.9 €ṡtCO2-1 (2.4 €ṡkg-1 and 50 €ṡtCO2-1, respectively, for SMR with CO2 capture) while for SE-SMR-SOFC the levelised cost of electricity is 0.078 €ṡkWh-1 and the cost of CO2 avoided is 36.9 €ṡtCO2-1 (0.080 €ṡkWh-1 and 80 €ṡtCO2-1, respectively, for natural gas-fired power plant with carbon capture). The sensitivity analysis showed that the specific cost of fuel and the capital cost of fuel cell mainly affect the economic performance of SE-SMR and SE-SMR-SOFC, respectively. The daily revenue of the SE-SMR-SOFC system is higher than that of the natural gas-fired power plant if the difference between the carbon tax and the CO2 transport and storage cost is > 6 €ṡtCO2-1.

Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

Science.gov (United States)

You, K.; Flemings, P. B.

2017-12-01

We quantitatively investigate the integral processes of methane hydrate formation from local microbial methane generation, burial of methane hydrate with sedimentation, and methane recycling at the base of the hydrate stability zone (BHSZ) with a multiphase multicomponent numerical model. Methane recycling happens in cycles, and there is not a steady state. Each cycle starts with free gas accumulation from hydrate dissociation below the BHSZ. This free gas flows upward under buoyancy, elevates the hydrate saturation and capillary entry pressure at the BHSZ, and this prevents more free gas flowing in. Later as this layer with elevated hydrate saturation is buried and dissociated, the large amount of free gas newly released and accumulated below rapidly intrudes into the hydrate stability zone, drives rapid hydrate formation and creates three-phase (gas, liquid and hydrate) equilibrium above the BHSZ. The gas front retreats to below the BHSZ until all the free gas is depleted. The shallowest depth that the free gas reaches in one cycle moves toward seafloor as more and more methane is accumulated to the BHSZ with time. More methane is stored above the BHSZ in the form of concentrated hydrate in sediments with relatively uniform pore throat, and/or with greater compressibility. It is more difficult to initiate methane recycling in passive continental margins where the sedimentation rate is low, and in sediments with low organic matter content and/or methanogenesis reaction rate. The presence of a permeable layer can store methane for significant periods of time without recycling. In a 2D system where the seafloor dips rapidly, the updip gas flow along the BHSZ transports more methane toward topographic highs where methane gas and elevated hydrate saturation intrude deeper into the hydrate stability zone within one cycle. This could lead to intermittent gas venting at seafloor at the topographic highs. This study provides insights on many phenomenon associated with

Methane potential of sterilized solid slaughterhouse wastes.

Science.gov (United States)

Pitk, Peep; Kaparaju, Prasad; Vilu, Raivo

2012-07-01

The aim of the current study was to determine chemical composition and methane potential of Category 2 and 3 solid slaughterhouse wastes rendering products (SSHWRP) viz. melt, decanter sludge, meat and bone meal (MBM), technical fat and flotation sludge from wastewater treatment. Chemical analyses showed that SSHWRP were high in protein and lipids with total solids (TS) content of 96-99%. Methane yields of the SSHWRP were between 390 and 978 m(3) CH(4)/t volatile solids (VS)(added). Based on batch experiments, anaerobic digestion of SSHWRP from the dry rendering process could recover 4.6 times more primary energy than the energy required for the rendering process. Estonia has technological capacity to sterilize all the produced Category 2 and 3 solid slaughterhouse wastes (SSHW) and if separated from Category 1 animal by-products (ABP), it could be further utilized as energy rich input material for anaerobic digestion. Copyright © 2012 Elsevier Ltd. All rights reserved.

Study of the methanization development potential in the Mayenne district (53)

International Nuclear Information System (INIS)

Duval, Valentin; Lemarie, Christophe; Geneau De Lamarliere, Laurent; Hubert, Cecile; Le Guen, Gaelle

2011-06-01

The first objective of this study is to determine the quantity of fermentable wastes produced by agricultural exploitations, agri-food industries and communities at the district scale, and to identify the main agricultural, industrial and community-based consumers of agricultural heat in order to ensure project profitability. A second objective, based on previous assessments, is to highlight possible methanization projects on the whole district territory, and to determine needed surfaces in relationship with the spreading of the digestate produced by these methanization projects. As far as the second objective is concerned, the report propose some generalities (project typologies, development criteria, produced energy, other potential wastes), presents different types of liquid phase or dry methanization (methodology, technology, costs), alternative scenarios, spreading potentials, and an environmental assessment (greenhouse emissions, impact on the natural and human environment). Several appendices are provided which contain data tables, maps of production assessments and of location distributions of installations

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

Steam reforming of heptane in a fluidized bed membrane reactor

Science.gov (United States)

Rakib, Mohammad A.; Grace, John R.; Lim, C. Jim; Elnashaie, Said S. E. H.

n-Heptane served as a model compound to study steam reforming of naphtha as an alternative feedstock to natural gas for production of pure hydrogen in a fluidized bed membrane reactor. Selective removal of hydrogen using Pd 77Ag 23 membrane panels shifted the equilibrium-limited reactions to greater conversion of the hydrocarbons and lower yields of methane, an intermediate product. Experiments were conducted with no membranes, with one membrane panel, and with six panels along the height of the reactor to understand the performance improvement due to hydrogen removal in a reactor where catalyst particles were fluidized. Results indicate that a fluidized bed membrane reactor (FBMR) can provide a compact reformer for pure hydrogen production from a liquid hydrocarbon feedstock at moderate temperatures (475-550 °C). Under the experimental conditions investigated, the maximum achieved yield of pure hydrogen was 14.7 moles of pure hydrogen per mole of heptane fed.

H2S mediated thermal and photochemical methane activation

Science.gov (United States)

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric

2013-01-01

Sustainable, low temperature methods of natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) in mixture with methane, CH4, altogether deemed as sub-quality or “sour” gas. We propose a unique method for activating this “sour” gas to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3, and an energy carrier, such as H2. For this purpose, we computationally investigated H2S mediated methane activation to form a reactive CH3SH species via direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4+H2S complex results in a barrier-less relaxation via a conical intersection to form a ground state CH3SH+H2 complex. The resulting CH3SH can further be heterogeneously coupled over acidic catalysts to form higher hydrocarbons while the H2 can be used as a fuel. This process is very different from a conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced controllability over the process conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the currently industrially used methane steam reforming (SMR). PMID:24150813

H2S-mediated thermal and photochemical methane activation.

Science.gov (United States)

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric V

2013-12-02

Sustainable, low-temperature methods for natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) mixed with methane, deemed altogether as sub-quality or "sour" gas. We propose a unique method of activation to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3 , and an energy carrier such as H2. For this purpose, we investigated the H2S-mediated methane activation to form a reactive CH3SH species by means of direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4 + H2S complex resulted in a barrierless relaxation by a conical intersection to form a ground-state CH3SH + H2 complex. The resulting CH3SH could further be coupled over acidic catalysts to form higher hydrocarbons, and the resulting H2 used as a fuel. This process is very different from conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced control over the conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the current industrial steam methane reforming (SMR). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Geraniol and Camphene on in Vitro Rumen Fermentation and Methane Production

Directory of Open Access Journals (Sweden)

Joch M.

2017-06-01

Full Text Available The objective of this study was to determine the effects of geraniol and camphene at three dosages (300, 600, and 900 mg l-1 on rumen microbial fermentation and methane emission in in vitro batch culture of rumen fluid supplied with a 60 : 40 forage : concentrate substrate (16.2% crude protein, 33.1% neutral detergent fibre. The ionophore antibiotic monensin (8 mg/l was used as positive control. Compared to control, geraniol significantly (P 0.05 methane production and slightly decreased (P < 0.05 VFA production. Due to the strong antimethanogenic effect of geraniol a careful selection of dose and combination with other antimethanogenic compounds may be effective in mitigating methane emission from ruminants. However, if a reduction in total VFA production and dry matter digestibility persisted in vivo, geraniol would have a negative effect on animal productivity.

Fluxed of nitrous oxide and methane in a lake border ecosystem in northern Germany

Energy Technology Data Exchange (ETDEWEB)

Rusch, H.; Rembges, D.; Papke, H.; Rennenberg, H. [Fraunhofer Inst. for Atmospheric Environmental Research, Garmisch-Partenkirchen (Germany)

1995-12-31

Methane and nitrous oxide are radiatively active trace gases. This accounts for approximately 20 % of the total anticipated greenhouse effect. The atmospheric mixing ratio of both gases has increased significantly during the last decades at a rate of 0.25 % yr{sup -l} for N{sub 2}O and a rate of 1 % yr{sup -1} for CH{sub 4}. Whether this increase is caused by enhanced biogenic production of both gases or is due to decreased global sinks, has not been definitely elucidated. Soils are an important source of methane and nitrous oxide. Natural wetlands, e.g., have a similar global source strength of methane as rice paddies. On the other hand, well aerated grasslands have been shown to be a sink for atmospheric methane due to methane oxidation. Nitrous oxide is emitted by a wide range of soil types. Its rate of emission is strongly enhanced by nitrogen fertilization. In the present study, fluxes of methane and nitrous oxide were determined in a lake border ecosystem along a toposequence from reed to dry pasture. The aim of this study was to characterize the influence of soil type, land use and season on the flux rates of these greenhouse gases. (author)

Fluxed of nitrous oxide and methane in a lake border ecosystem in northern Germany

Energy Technology Data Exchange (ETDEWEB)

Rusch, H; Rembges, D; Papke, H; Rennenberg, H [Fraunhofer Inst. for Atmospheric Environmental Research, Garmisch-Partenkirchen (Germany)

1996-12-31

Methane and nitrous oxide are radiatively active trace gases. This accounts for approximately 20 % of the total anticipated greenhouse effect. The atmospheric mixing ratio of both gases has increased significantly during the last decades at a rate of 0.25 % yr{sup -l} for N{sub 2}O and a rate of 1 % yr{sup -1} for CH{sub 4}. Whether this increase is caused by enhanced biogenic production of both gases or is due to decreased global sinks, has not been definitely elucidated. Soils are an important source of methane and nitrous oxide. Natural wetlands, e.g., have a similar global source strength of methane as rice paddies. On the other hand, well aerated grasslands have been shown to be a sink for atmospheric methane due to methane oxidation. Nitrous oxide is emitted by a wide range of soil types. Its rate of emission is strongly enhanced by nitrogen fertilization. In the present study, fluxes of methane and nitrous oxide were determined in a lake border ecosystem along a toposequence from reed to dry pasture. The aim of this study was to characterize the influence of soil type, land use and season on the flux rates of these greenhouse gases. (author)

Methane cycling. Nonequilibrium clumped isotope signals in microbial methane.

Science.gov (United States)

Wang, David T; Gruen, Danielle S; Lollar, Barbara Sherwood; Hinrichs, Kai-Uwe; Stewart, Lucy C; Holden, James F; Hristov, Alexander N; Pohlman, John W; Morrill, Penny L; Könneke, Martin; Delwiche, Kyle B; Reeves, Eoghan P; Sutcliffe, Chelsea N; Ritter, Daniel J; Seewald, Jeffrey S; McIntosh, Jennifer C; Hemond, Harold F; Kubo, Michael D; Cardace, Dawn; Hoehler, Tori M; Ono, Shuhei

2015-04-24

Methane is a key component in the global carbon cycle, with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply substituted "clumped" isotopologues (for example, (13)CH3D) has recently emerged as a proxy for determining methane-formation temperatures. However, the effect of biological processes on methane's clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on (13)CH3D abundances and results in anomalously elevated formation-temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters. Copyright © 2015, American Association for the Advancement of Science.

Urea plus nitrate pretreatment of rice and wheat straws enhances degradation and reduces methane production in in vitro ruminal culture.

Science.gov (United States)

Zhang, Xiumin; Wang, Min; Wang, Rong; Ma, Zhiyuan; Long, Donglei; Mao, Hongxiang; Wen, Jiangnan; Bernard, Lukuyu A; Beauchemin, Karen A; Tan, Zhiliang

2018-04-10

Urea pretreatment of straw damages fiber structure, while nitrate supplementation of ruminal diets inhibits enteric methane production. The study examined the combined effects of these treatments on ruminal substrate biodegradation and methane production using an in vitro incubation system. Rice and wheat straws were pretreated with urea (40 g kg -1 straw dry matter, DM) and urea + ammonium nitrate (34 + 6 g kg -1 dry matter (DM), respectively), and each straw (control, urea, urea+nitrate) was used in batch culture incubations in three replications (runs). Urea pretreatment increased (P content (+17%) and in vitro DM degradation of rice straw, in comparison with control. Urea+nitrate pretreatment of rice and wheat straws had higher (P content, in vitro DM degradation and propionate molar proportion, and lower (P ruminal biodegradation, facilitate propionate production and reduce methane production from lignified straws. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Revisiting factors controlling methane emissions from high-Arctic tundra

DEFF Research Database (Denmark)

Mastepanov, M.; Sigsgaard, C.; Tagesson, T.

2013-01-01

controlling methane emission, i.e. temperature and water table position. Late in the growing season CH4 emissions were found to be very similar between the study years (except the extremely dry 2010) despite large differences in climatic factors (temperature and water table). Late-season bursts of CH4...... short-term control factors (temperature and water table). Our findings suggest the importance of multiyear studies with a continued focus on shoulder seasons in Arctic ecosystems....

Landscape-level terrestrial methane flux observed from a very tall tower

Science.gov (United States)

Desai, Ankur R.; Xu, Ke; Tian, Hanqin; Weishampel, Peter; Thom, Jonthan; Baumann, Daniel D.; Andrews, Arlyn E.; Cook, Bruce D.; King, Jennifer Y.; Kolka, Randall

2015-01-01

Simulating the magnitude and variability of terrestrial methane sources and sinks poses a challenge to ecosystem models because the biophysical and biogeochemical processes that lead to methane emissions from terrestrial and freshwater ecosystems are, by their nature, episodic and spatially disjunct. As a consequence, model predictions of regional methane emissions based on field campaigns from short eddy covariance towers or static chambers have large uncertainties, because measurements focused on a particular known source of methane emission will be biased compared to regional estimates with regards to magnitude, spatial scale, or frequency of these emissions. Given the relatively large importance of predicting future terrestrial methane fluxes for constraining future atmospheric methane growth rates, a clear need exists to reduce spatiotemporal uncertainties. In 2010, an Ameriflux tower (US-PFa) near Park Falls, WI, USA, was instrumented with closed-path methane flux measurements at 122 m above ground in a mixed wetland–upland landscape representative of the Great Lakes region. Two years of flux observations revealed an average annual methane (CH4) efflux of 785 ± 75 mg CCH4 m−2 yr−1, compared to a mean CO2 sink of −80 g CCO2 m−2 yr−1, a ratio of 1% in magnitude on a mole basis. Interannual variability in methane flux was 30% of the mean flux and driven by suppression of methane emissions during dry conditions in late summer 2012. Though relatively small, the magnitude of the methane source from the very tall tower measurements was mostly within the range previously measured using static chambers at nearby wetlands, but larger than a simple scaling of those fluxes to the tower footprint. Seasonal patterns in methane fluxes were similar to those simulated in the Dynamic Land Ecosystem Model (DLEM), but magnitude depends on model parameterization and input data, especially regarding wetland extent. The model was unable to simulate short

Direct Hysteresis Heating of Catalytically Active Ni–Co Nanoparticles as Steam Reforming Catalyst

DEFF Research Database (Denmark)

Mortensen, Peter Mølgaard; Engbæk, Jakob Soland; Vendelbo, Søren Bastholm

2017-01-01

We demonstrated a proof-of-concept catalytic steam reforming flow reactor system heated only by supported magnetic nickel–cobalt nanoparticles in an oscillating magnetic field. The heat transfer was facilitated by the hysteresis heating in the nickel–cobalt nanoparticles alone. This produced...... a sufficient power input to equilibrate the reaction at above 780 °C with more than 98% conversion of methane. The high conversion of methane indicated that Co-rich nanoparticles with a high Curie temperature provide sufficient heat to enable the endothermic reaction, with the catalytic activity facilitated...... by the Ni content in the nanoparticles. The magnetic hysteresis losses obtained from temperature-dependent hysteresis measurements were found to correlate well with the heat generation in the system. The direct heating of the catalytic system provides a fast heat transfer and thereby overcomes the heat...

Additive effect of Ce, Mo and K to nickel-cobalt aluminate supported solid oxide fuel cell for direct internal reforming of methane

International Nuclear Information System (INIS)

Kwak, Bu Ho; Park, Jungdeok; Yoon, Heechul; Kim, Hyeon Hui; Kim, Lim; Chung, Jong Shik

2014-01-01

Direct internal reforming of methane (steam/carbon=0.031, 850 .deg. C) is tested using button cells of Ni-YSZ/YSZ/LSM in which the anode layer is supported either on Ni-YSZ or on Ni-CoAl 2 O 4 . The Ni-CoAl 2 O 4 supported cell shows little degradation with operating time, as a result of higher resistance against carbon deposition, whereas the Ni-YSZ supported cell deactivates quickly and suffers fracture in 50 h. Upon incorporation of additives such as K, Ce, or Mo into the Ni-CoAl 2 O 4 support, cells with 0.5 wt% CeO 2 exhibit the best stable performance as a result of reduced coke formation. Cells with 0.5 wt% Mo exhibit the lowest performance. Although no carbon deposit is detected in the cells with K 2 CO 3 additives, their performance is worse than that in the CeO 2 case, and, in constant-current mode, there is a sudden voltage drop to zero after a certain period of time; this time becomes shorter with increasing K content. The injection of potassium into the anode side facilitates the generation of OH - and CO 3 2- in the anode and promotes the diffusion of these ions to the cathode. Increased polarization resistance at the cathode and increased electrolyte resistance result in such a sudden failure

Assessing the Life-Cycle Performance of Hydrogen Production via Biofuel Reforming in Europe

Directory of Open Access Journals (Sweden)

Ana Susmozas

2015-06-01

Full Text Available Currently, hydrogen is mainly produced through steam reforming of natural gas. However, this conventional process involves environmental and energy security concerns. This has led to the development of alternative technologies for (potentially green hydrogen production. In this work, the environmental and energy performance of biohydrogen produced in Europe via steam reforming of glycerol and bio-oil is evaluated from a life-cycle perspective, and contrasted with that of conventional hydrogen from steam methane reforming. Glycerol as a by-product from the production of rapeseed biodiesel and bio-oil from the fast pyrolysis of poplar biomass are considered. The processing plants are simulated in Aspen Plus® to provide inventory data for the life cycle assessment. The environmental impact potentials evaluated include abiotic depletion, global warming, ozone layer depletion, photochemical oxidant formation, land competition, acidification and eutrophication. Furthermore, the cumulative (total and non-renewable energy demand is calculated, as well as the corresponding renewability scores and life-cycle energy balances and efficiencies of the biohydrogen products. In addition to quantitative evidence of the (expected relevance of the feedstock and impact categories considered, results show that poplar-derived bio-oil could be a suitable feedstock for steam reforming, in contrast to first-generation bioglycerol.

Methane Production of Full-Scale Anaerobic Digestion Plants Calculated from Substrate’s Biomethane Potentials Compares Well with the One Measured On-Site

Energy Technology Data Exchange (ETDEWEB)

Holliger, Christof, E-mail: christof.holliger@epfl.ch [Laboratory for Environmental Biotechnology, School for Architecture, Civil and Environmental Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Fruteau de Laclos, Hélène [Methaconsult, Préverenges (Switzerland); Hack, Gabrielle [Laboratory for Environmental Biotechnology, School for Architecture, Civil and Environmental Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland)

2017-06-09

Biomethane potential (BMP) tests are used to determine the amount of methane that can be produced from organic materials in order to design different components of full-scale anaerobic digestion (AD) plants such as size of the digesters and units exploiting the produced biogas. However, little is known on how well BMPs compare with biogas production from the same organic materials in full-scale installations. In this study, two AD plants were chosen to carry out such comparisons, a dry AD plant treating green waste from urban areas and food waste from restaurants and supermarkets, and a liquid AD plant treating waste sludge from wastewater treatment and seven additional organic wastes. The BMPs of multiple samples of the individual organic materials collected during a period of 7–9 months were determined. Separate tests of mixtures of organic materials confirmed that the BMP of the mixtures can be calculated by adding the BMPs of the individual materials. The weekly methane production during the investigated periods was calculated from the full-scale installation data on the feeding of the digesters and the BMPs of each substrate fed into the digesters and compared with the weekly methane production measured on-site. The latter was calculated from the most accurately measured entity, either the electricity or the volume of purified biomethane injected into the grid. The weekly methane production rates calculated from BMPs and the one measured on-site were very similar and followed the same pattern. Some exceptions could be explained by, e.g., an overload of the full-scale installation. The measured weekly methane production accounted for 94.0 ± 6.8 and 89.3 ± 5.7% of the calculated weekly methane production for the wet and dry AD plant, respectively. For 26 out of 29 weeks, the calculated weekly methane production overestimated the measured one in the case of the wet AD plant and for 37 out of 39 weeks for the dry AD plant. Based on these results, it is

Methane Production of Full-Scale Anaerobic Digestion Plants Calculated from Substrate’s Biomethane Potentials Compares Well with the One Measured On-Site

International Nuclear Information System (INIS)

Holliger, Christof; Fruteau de Laclos, Hélène; Hack, Gabrielle

2017-01-01

Biomethane potential (BMP) tests are used to determine the amount of methane that can be produced from organic materials in order to design different components of full-scale anaerobic digestion (AD) plants such as size of the digesters and units exploiting the produced biogas. However, little is known on how well BMPs compare with biogas production from the same organic materials in full-scale installations. In this study, two AD plants were chosen to carry out such comparisons, a dry AD plant treating green waste from urban areas and food waste from restaurants and supermarkets, and a liquid AD plant treating waste sludge from wastewater treatment and seven additional organic wastes. The BMPs of multiple samples of the individual organic materials collected during a period of 7–9 months were determined. Separate tests of mixtures of organic materials confirmed that the BMP of the mixtures can be calculated by adding the BMPs of the individual materials. The weekly methane production during the investigated periods was calculated from the full-scale installation data on the feeding of the digesters and the BMPs of each substrate fed into the digesters and compared with the weekly methane production measured on-site. The latter was calculated from the most accurately measured entity, either the electricity or the volume of purified biomethane injected into the grid. The weekly methane production rates calculated from BMPs and the one measured on-site were very similar and followed the same pattern. Some exceptions could be explained by, e.g., an overload of the full-scale installation. The measured weekly methane production accounted for 94.0 ± 6.8 and 89.3 ± 5.7% of the calculated weekly methane production for the wet and dry AD plant, respectively. For 26 out of 29 weeks, the calculated weekly methane production overestimated the measured one in the case of the wet AD plant and for 37 out of 39 weeks for the dry AD plant. Based on these results, it is

Solar Reforming of Carbon Dioxide to Produce Diesel Fuel

Energy Technology Data Exchange (ETDEWEB)

Dennis Schuetzle; Robert Schuetzle

2010-12-31

This project focused on the demonstration of an innovative technology, referred to as the Sunexus CO2 Solar Reformer, which utilizes waste CO2 as a feedstock for the efficient and economical production of synthetic diesel fuel using solar thermal energy as the primary energy input. The Sunexus technology employs a two stage process for the conversion of CO2 to diesel fuel. A solar reforming system, including a specially designed reactor and proprietary CO2 reforming catalyst, was developed and used to convert captured CO2 rich gas streams into syngas (primarily hydrogen and carbon monoxide) using concentrated solar energy at high conversion efficiencies. The second stage of the system (which has been demonstrated under other funding) involves the direct conversion of the syngas into synthetic diesel fuel using a proprietary catalyst (Terra) previously developed and validated by Pacific Renewable Fuels and Chemicals (PRFC). The overall system energy efficiency for conversion of CO2 to diesel fuel is 74%, due to the use of solar energy. The results herein describe modeling, design, construction, and testing of the Sunexus CO2 Solar Reformer. Extensive parametric testing of the solar reformer and candidate catalysts was conducted and chemical kinetic models were developed. Laboratory testing of the Solar Reformer was successfully completed using various gas mixtures, temperatures, and gas flow rates/space velocities to establish performance metrics which can be employed for the design of commercial plants. A variety of laboratory tests were conducted including dry reforming (CO2 and CH{sub 4}), combination dry/steam reforming (CO2, CH{sub 4} & H{sub 2}O), and tri-reforming (CO2, CH{sub 4}, H{sub 2}O & O{sub 2}). CH{sub 4} and CO2 conversions averaged 95-100% and 50-90% per reformer cycle, respectively, depending upon the temperatures and gas space velocities. No formation of carbon deposits (coking) on the catalyst was observed in any of these tests. A 16 ft. diameter

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

Electrical resistivity tomography to quantify in situ liquid content in a full-scale dry anaerobic digestion reactor.

Science.gov (United States)

André, L; Lamy, E; Lutz, P; Pernier, M; Lespinard, O; Pauss, A; Ribeiro, T

2016-02-01

The electrical resistivity tomography (ERT) method is a non-intrusive method widely used in landfills to detect and locate liquid content. An experimental set-up was performed on a dry batch anaerobic digestion reactor to investigate liquid repartition in process and to map spatial distribution of inoculum. Two array electrodes were used: pole-dipole and gradient arrays. A technical adaptation of ERT method was necessary. Measured resistivity data were inverted and modeled by RES2DINV software to get resistivity sections. Continuous calibration along resistivity section was necessary to understand data involving sampling and physicochemical analysis. Samples were analyzed performing both biochemical methane potential and fiber quantification. Correlations were established between the protocol of reactor preparation, resistivity values, liquid content, methane potential and fiber content representing liquid repartition, high methane potential zones and degradations zones. ERT method showed a strong relevance to monitor and to optimize the dry batch anaerobic digestion process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

Science.gov (United States)

Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

2015-01-01

Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

CHARM COST-EFFECTIVE HIGH-EFFICIENCY ADVANCED REFORMING MODULE FINAL TECHNICAL REPORT

Energy Technology Data Exchange (ETDEWEB)

Pollica, Darryl; Cross, James C; Sharma, Atul; Shi, Yanlong; Clawson, Lawrence; O' Brien, Chris; Gilhooly, Kara; Kim, Changsik; Quet, Pierre-Francois

2009-09-02

Background Creation of a hydrogen infrastructure is an important prerequisite of widespread fuel cell commercialization, especially for the automotive market. Hydrogen is an attractive fuel since it offers an opportunity to replace petroleum-based fuels, but hydrogen occurs naturally only in chemical compounds like water or hydrocarbons that must be chemically converted to produce it. While an ultimate goal is to produce hydrogen through renewable energy sources, steam methane reforming (SMR) of natural gas is currently the most economical solution to initiate the transition to a hydrogen economy. Centralized hydrogen generation using large industrial SMR plants is already in place to serve customers. Yet, because of the weight and size of cylinders needed to contain hydrogen gas or liquid, transportation of hydrogen may only be economical for short distances. Consequently, distributed natural gas reforming, which trades off the economies of scale of large plants for simplified delivery logistics, is an attractive alternative that could address immediate problems with the lack of hydrogen infrastructure.

Anaerobic digestion of industrial hemp-effect of harvest time on methane energy yield per hectare

Energy Technology Data Exchange (ETDEWEB)

Kreuger, E; Escobar, F; Bjoernsson, L [Department of Biotechnology, Lund University, P.O. Box 124, SE-221 00 Lund (Sweden); Prade, T; Svensson, S -E; Englund, J -E [Department of Agriculture-Farming Systems, Technology and Product Quality, Swedish University of Agricultural Sciences, P.O. Box 104, SE-230 53 Alnarp (Sweden)

2011-02-15

There is a worldwide emphasis to increase the share of renewable transportation fuels. When using agricultural land for production of renewable transportation fuels, the energy output per hectare for different crops and transportation fuels is a crucial factor. In this study, the gross methane energy yield per hectare from anaerobic digestion of industrial hemp (Cannabis sativa L.), was determined at four different harvest times between July and October in Southern Sweden, a cold climate region. The biomass yield was determined for three years and the methane yield was determined for two years through the biochemical methane potential test. The highest biomass yield, 16 tonnes dry matter per hectare on an average, and the highest methane energy yield per hectare was achieved when the hemp was harvested in September or October, with an average gross methane energy yield of 136 {+-} 24 GJ per hectare. There was no significant difference in the specific methane yield between the harvest times; the average being 234 {+-} 35 m{sup 3} per tonne volatile solids. Biogas from hemp turned out to be a high yielding alternative to the currently dominating renewable transportation fuels produced from crops grown in Sweden: ethanol from wheat and biodiesel from rapeseed. (author)

A source of methane from upland forests in the Brazilian Amazon.

Science.gov (United States)

Janaina Braga do Carmo; Michael Keller; Jadson Dezincourt Dias; Plinio Barbosa de Camargo; Patrick Crill

2006-01-01

We sampled air in the canopy layer of undisturbed upland forests during wet and dry seasons at three sites in the Brazilian Amazon region and found that both methane(CH4) and carbon dioxide (CO2) mixing ratios increased at night. Such increases were consistent across sites and seasons. A canopy layer budget model based on measured soil-atmosphere fluxes of CO2 was...

In vitro evaluation of different varieties of maize fodder for their methane generation potential and digestibility with goat rumen liquor

Directory of Open Access Journals (Sweden)

Shalini Vaswani

2016-11-01

Full Text Available Aim: To evaluate the methane generation potential and digestibility of different (normal and three high-quality protein maize [HQPM] varieties of maize fodder with goat rumen liquor in vitro. Materials and Methods: Methane production potential and digestibility of different varieties of maize fodder were tested in in vitro gas production test. Seven varieties of maize, four normal (HTHM 5101, DHM 117, HM 5, and Shaktiman/900 M Gold, and three high-quality protein (HQPM 5, HQPM 7, and HQPM 9/Vivek were grown in different plots under the same environmental and agro-climatic conditions. Fodders were harvested at 45-50 days of sowing, and the representative samples of fodder from different varieties of maize were collected for analysis. Dried and grinded form of these maize fodder varieties was tested for gas, methane, and digestibility using goat rumen microflora in in vitro gas syringes. Results: Gas production (ml/g dry matter [DM] was highest for HM5 variety (97.66, whereas lowest for HQPM 9 variety (64.22. Gas production (ml/g degraded DM [DDM] and methane (% were statistically similar in different varieties of maize fodder. The methane production expressed as ml/g DM and ml/g DDM was significantly (p<0.05 highest for HM 5 (14.22 and 26.62 and lowest for DHM 117 variety (7.47 and 14.13. The in vitro DM digestibility (% and in vitro organic matter digestibility (% varied from 47.48 (HQPM 5 to 52.05 (HQPM 9 and 50.03 (HQPM 7 to 54.22 (HM 5, respectively. Conclusion: The present study concluded that DHM 117 maize variety fodder has lowest methane generation potential and incorporating it in the dietary regime of ruminants may contribute to lower methane production.

Measures of methane production and their phenotypic relationships with dry matter intake, growth, and body composition traits in beef cattle.

Science.gov (United States)

Herd, R M; Arthur, P F; Donoghue, K A; Bird, S H; Bird-Gardiner, T; Hegarty, R S

2014-11-01

Ruminants contribute up to 80% of greenhouse gas (GHG) emissions from livestock, and enteric methane production by ruminants is the main source of these GHG emissions. Hence, reducing enteric methane production is essential in any GHG emissions reduction strategy in livestock. Data from 2 performance-recording research herds of Angus cattle were used to evaluate a number of methane measures that target methane production (MPR) independent of feed intake and to examine their phenotypic relationships with growth and body composition. The data comprised 777 young bulls and heifers that were fed a roughage diet (ME of 9 MJ/kg DM) at 1.2 times their maintenance energy requirements and measured for MP in open circuit respiration chambers for 48 h. Methane traits evaluated included DMI during the methane measurement period, MPR, and methane yield (MY; MPR/DMI), with means (± SD) of 6.2 ± 1.4 kg/d, 187 ± 38 L/d, and 30.4 ± 3.5 L/kg, respectively. Four forms of residual MPR (RMP), which is a measure of actual minus predicted MPR, were evaluated. For the first 3 forms, predicted MPR was calculated using published equations. For the fourth (RMPR), predicted MPR was obtained by regression of MPR on DMI. Growth traits evaluated were BW at birth, weaning (200 d of age), yearling age (400 d of age), and 600 d of age, with means (± SD) of 34 ± 4.6, 238 ± 37, 357 ± 45, and 471 ± 53 kg, respectively. Body composition traits included ultrasound measures (600 d of age) of rib fat, rump fat, and eye muscle area, with means (± SD) of 3.8 ± 2.6 mm, 5.4 ± 3.8 mm, and 61 ± 7.7 cm(2), respectively. Methane production was positively correlated (r ± SE) with DMI (0.65 ± 0.02), MY (0.72 ± 0.02), the RMP traits (r from 0.65 to 0.79), the growth traits (r from 0.19 to 0.57), and the body composition traits (r from 0.13 to 0.29). Methane yield was, however, not correlated (r ± SE) with DMI (-0.02 ± 0.04) as well as the growth (r from -0.03 to 0.11) and body composition (r from 0

Contribution of Ruminal Fungi, Archaea, Protozoa, and Bacteria to the Methane Suppression Caused by Oilseed Supplemented Diets.

Science.gov (United States)

Wang, Shaopu; Giller, Katrin; Kreuzer, Michael; Ulbrich, Susanne E; Braun, Ueli; Schwarm, Angela

2017-01-01

Dietary lipids can suppress methane emission from ruminants, but effects are variable. Especially the role of bacteria, archaea, fungi and protozoa in mediating the lipid effects is unclear. In the present in vitro study, archaea, fungi and protozoa were selectively inhibited by specific agents. This was fully or almost fully successful for fungi and protozoa as well as archaeal activity as determined by the methyl-coenzyme M reductase alpha subunit gene. Five different microbial treatments were generated: rumen fluid being intact (I), without archaea (-A), without fungi (-F), without protozoa (-P) and with bacteria only (-AFP). A forage-concentrate diet given alone or supplemented with crushed full-fat oilseeds of either safflower ( Carthamus tinctorius ) or poppy ( Papaver somniferum ) or camelina ( Camelina sativa ) at 70 g oil kg -1 diet dry matter was incubated. This added up to 20 treatments with six incubation runs per treatment. All oilseeds suppressed methane emission compared to the non-supplemented control. Compared to the non-supplemented control, -F decreased organic matter (OM) degradation, and short-chain fatty acid concentration was greater with camelina and safflower seeds. Methane suppression per OM digested in -F was greater with camelina seeds (-12 vs.-7% with I, P = 0.06), but smaller with poppy seeds (-4 vs. -8% with I, P = 0.03), and not affected with safflower seeds. With -P, camelina seeds decreased the acetate-to-propionate ratio and enhanced the methane suppression per gram dry matter (18 vs. 10% with I, P = 0.08). Hydrogen recovery was improved with -P in any oilseeds compared to non-supplemented control. No methane emission was detected with the -A and -AFP treatments. In conclusion, concerning methanogenesis, camelina seeds seem to exert effects only on archaea and bacteria. By contrast, with safflower and poppy seeds methane was obviously reduced mainly through the interaction with protozoa or archaea associated with protozoa. This

Inhibition of methane oxidation in slurry surface crust by inorganic nitrogen

DEFF Research Database (Denmark)

Duan, Yun-Feng; Elsgaard, Lars; Petersen, Søren O

2013-01-01

Livestock slurry is an important source of methane (CH4). Depending on dry matter content, a floating crust may form where methane-oxidizing bacteria (MOB) and CH4 oxidation activity have been found, suggesting that surface crusts may reduce CH4 emissions from slurry. However, it is not known how...... MOB in this environment interact with inorganic nitrogen (N). We studied inhibitory effects of ammonium (NH4+), nitrate (NO3–) and nitrite (NO2–) on potential CH4 oxidation in a cattle slurry surface crust. Methane oxidation was assayed at salt concentrations up to 500 mM at 100 and 10,000 ppmv...... headspace CH4. First-order rate constants were used to evaluate the strength of inhibition. Nitrite was the most potent inhibitor, reducing methanotrophic activity by up to 70% at only 1 mM NO2–. MOB were least sensitive to NO3–, tolerating up to 30 mM NO3– at 100 ppmv CH4 and 50 mM NO3– at 10,000 ppmv CH4...

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

The effect of moisture on the methane adsorption capacity of shales: A study case in the eastern Qaidam Basin in China

Science.gov (United States)

Wang, Lu; Yu, Qingchun

2016-11-01

This study investigated the effects of moisture on high-pressure methane adsorption in carboniferous shales from the Qaidam Basin, China. The shale characteristics, including the organic/inorganic compositions and pore structure (volume and surface) distribution, were obtained using various techniques. Gibbs adsorption measurements were performed over a pressure range up to 6 MPa and temperatures of 308.15 K on dry samples and moisture-equilibrated samples to analyze the correlations between organic/inorganic matter, pore structure, and moisture content on the methane sorption capacity. Compared to dry samples, the sorption capacity of wet samples (0.44-2.52% of water content) is reduced from 19.7 ± 5.3% to 36.1% ± 6.1%. Langmuir fitting is conducted to investigate moisture-dependent variations of adsorbed methane density, Langmuir pressure, and volume. By combining the pore volume and surface distribution analyses, our observations suggested that the main competition sites for CH4-H2O covered pores of approximately 2-7 nm, whereas the effective sites for methane and water were predominantly distributed within smaller (10 nm), respectively. Regarding the compositional correlations, the impact of moisture on the amount of adsorbed methane shows a roughly linearly decreasing trend with increasing TOC content ranging from 0.62 to 2.88%, whereas the correlation between the moisture effect and various inorganic components is more complicated. Further fitting results indicate that illite/smectite mixed formations are closely related to the methane capacity, whereas the illite content show an evident connection to the pore structural (volume and surface) variations in the presence of moisture.

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  |  

Differing effects of 2 active dried yeast (Saccharomyces cerevisiae) strains on ruminal acidosis and methane production in nonlactating dairy cows.

Science.gov (United States)

Chung, Y-H; Walker, N D; McGinn, S M; Beauchemin, K A

2011-05-01

Fifteen ruminally cannulated, nonlactating Holstein cows were used to measure the effects of 2 strains of Saccharomyces cerevisiae, fed as active dried yeasts, on ruminal pH and fermentation and enteric methane (CH(4)) emissions. Nonlactating cows were blocked by total duration (h) that their ruminal pH was below 5.8 during a 6-d pre-experimental period. Within each block, cows were randomly assigned to control (no yeast), yeast strain 1 (Levucell SC), or yeast strain 2 (a novel strain selected for enhanced in vitro fiber degradation), with both strains (Lallemand Animal Nutrition, Montréal, QC, Canada) providing 1 × 10(10) cfu/head per day. Cows were fed once daily a total mixed ration consisting of a 50:50 forage to concentrate ratio (dry matter basis). The yeast strains were dosed via the rumen cannula daily at the time of feeding. During the 35-d experiment, ruminal pH was measured continuously for 7 d (d 22 to 28) by using an indwelling system, and CH(4) gas was measured for 4 d (d 32 to 35) using the sulfur hexafluoride tracer gas technique (with halters and yokes). Rumen contents were sampled on 2 d (d 22 and 26) at 0, 3, and 6h after feeding. Dry matter intake, body weight, and apparent total-tract digestibility of nutrients were not affected by yeast feeding. Strain 2 decreased the average daily minimum (5.35 vs. 5.65 or 5.66), mean (5.98 vs. 6.24 or 6.34), and maximum ruminal pH (6.71 vs. 6.86 or 6.86), and prolonged the time that ruminal pH was below 5.8 (7.5 vs. 3.3 or 1.0 h/d) compared with the control or strain 1, respectively. The molar percentage of acetate was lower and that of propionate was greater in the ruminal fluid of cows receiving strain 2 compared with cows receiving no yeast or strain 1. Enteric CH(4) production adjusted for intake of dry matter or gross energy, however, did not differ between either yeast strain compared with the control but it tended to be reduced by 10% when strain 2 was compared with strain 1. The study shows that

Measurements and modeling to quantify emissions of methane and VOCs from shale gas operations: Final Report

Energy Technology Data Exchange (ETDEWEB)

Presto, Albert A [Carnegie Mellon Univ., Pittsburgh, PA (United States)

2017-06-30

The objectives of the project were to determine the leakage rates of methane and ozone-forming Volatile Organic Compounds (VOCs) and the emission rates of air toxics from Marcellus shale gas activities. Methane emissions in the Marcellus Shale region were differentiated between “newer” sources associated with shale gas development and “older” sources associated with coal or conventional natural gas exploration. This project conducted measurements of methane and VOC emissions from both shale and non-shale natural gas resources. The initial scope of the project was the Marcellus Shale basin, and measurements were conducted in both the western wet gas regions (southwest PA and WV) and eastern dry gas region (northeast PA) of the basin. During this project, we obtained additional funding from other agencies to expand the scope of measurements to include additional basins. The data from both the Marcellus and other basins were combined to construct a national analysis of methane emissions from oil & gas production activities.

Chemical composition and methane yield of reed canary grass as influenced by harvesting time and harvest frequency

DEFF Research Database (Denmark)

Kandel, Tanka Prasad; Sutaryo, Sutaryo; Møller, Henrik Bjarne

2013-01-01

This study examined the influence of harvest time on biomass yield, dry matter partitioning, biochemical composition and biological methane potential of reed canary grass harvested twice a month in one-cut (OC) management. The regrowth of biomass harvested in summer was also harvested in autumn...... as a two-cut management with (TC-F) or without (TC-U) fertilization after summer harvest. The specific methane yields decreased significantly with crop maturity that ranged from 384 to 315 and from 412 to 283 NL (normal litre) (kg VS)-1 for leaf and stem, respectively. Approximately 45% more methane...... was produced by the TC-F management (5430 Nm3 ha-1) as by the OC management (3735 Nm3 ha-1). Specific methane yield was moderately correlated with the concentrations of fibre components in the biomass. Larger quantity of biogas produced at the beginning of the biogas assay from early harvested biomass...

Selective control of reformed composition of n-heptane via plasma chemistry

KAUST Repository

Manoj Kumar Reddy, P.

2016-08-23

This paper presents experimental results for reforming n-heptane in a temperature-controlled dielectric barrier discharge reactor to show detailed chemical composition in the products and to propose a potential method to control the product composition. Reformed products of n-heptane and water mixture in an inert Ar feed could be identified as hydrogen, carbon monoxide, oxygenates, and various hydrocarbons, having a wide range of carbon numbers. To selectively increase production of short-chain hydrocarbons, Ar was replaced by CH4. An increased pool of methyl radicals, via plasma chemistry of CH4, might facilitate to stabilize intermediate alkyls (R) into RCH3, which successfully increased short-chain hydrocarbon concentration. When CO2 was supplied instead of Ar (to provide enriched OH and O radicals), significantly higher oxygenate concentrations were obtained through the stabilization of alkyls as ROH (alcohol), and RC([Formula presented])R′ (ketone). The use of methane and carbon dioxide as feed to tailor the products of plasma-assisted reforming of n-heptane with methyl (CH3), or O radicals, is successfully demonstrated in the presence of water vapor. Detailed product analysis, such as product selection, rates and energy efficiency using a gas chromatograph and a gas chromatography mass spectrometer, will be elaborated upon. © 2016 Elsevier Ltd

Chemical composition and methane yield of reed canary grass as influenced by harvesting time and harvest frequency.

Science.gov (United States)

Kandel, Tanka P; Sutaryo, Sutaryo; Møller, Henrik B; Jørgensen, Uffe; Lærke, Poul E

2013-02-01

This study examined the influence of harvest time on biomass yield, dry matter partitioning, biochemical composition and biological methane potential of reed canary grass harvested twice a month in one-cut (OC) management. The regrowth of biomass harvested in summer was also harvested in autumn as a two-cut management with (TC-F) or without (TC-U) fertilization after summer harvest. The specific methane yields decreased significantly with crop maturity that ranged from 384 to 315 and from 412 to 283 NL (normal litre) (kgVS)(-1) for leaf and stem, respectively. Approximately 45% more methane was produced by the TC-F management (5430Nm(3)ha(-1)) as by the OC management (3735Nm(3)ha(-1)). Specific methane yield was moderately correlated with the concentrations of fibre components in the biomass. Larger quantity of biogas produced at the beginning of the biogas assay from early harvested biomass was to some extent off-set by lower concentration of methane. Copyright © 2012 Elsevier Ltd. All rights reserved.

Steam conversion of liquefied petroleum gas and methane in microchannel reactor

Science.gov (United States)

Dimov, S. V.; Gasenko, O. A.; Fokin, M. I.; Kuznetsov, V. V.

2018-03-01

This study presents experimental results of steam conversion of liquefied petroleum gas and methane in annular catalytic reactor - heat exchanger. The steam reforming was done on the Rh/Al2O3 nanocatalyst with the heat applied through the microchannel gap from the outer wall. Concentrations of the products of chemical reactions in the outlet gas mixture are measured at different temperatures of reactor. The range of channel wall temperatures at which the ratio of hydrogen and carbon oxide in the outlet mixture grows substantially is determined. Data on the composition of liquefied petroleum gas conversion products for the ratio S/C = 5 was received for different GHVS.

Greenhouse gas microbiology in wet and dry straw crust covering pig slurry

DEFF Research Database (Denmark)

Hansen, Rikke Ruth; Nielsen, Daniel Aagren; Schramm, Andreas

2009-01-01

was observed in all crusted treatments exposed to anoxia, and this was probably a result of denitrification based on NO2- and NO3- that had accumulated in the crust during oxic conditions. To reduce overall greenhouse gas emissions, floating crust should be managed to optimize conditions for methanotrophs....... microbiology had an effect on the emission of the potent greenhouse gases CH4 and nitrous oxide (N2O) when crust moisture was manipulated ("Dry", "Moderate", and "Wet"). The dry crust had the deepest oxygen penetration (45 mm as compared to 20 mm in the Wet treatment) as measured with microsensors, the highest...... oxidizing bacteria were undetectable and methane oxidizing bacteria were only sparsely present in the "Wet" treatment. A change to anoxia did not affect the CH4 emission indicating the virtual absence of aerobic methane oxidation in the investigated 2-months old crusts. However, an increase in N2O emission...

Electrochemical evaluation of sulfur poisoning in a methane-fuelled solid oxide fuel cell: Effect of current density and sulfur concentration

DEFF Research Database (Denmark)

Hagen, Anke; Johnson, Gregory B.; Hjalmarsson, Per

2014-01-01

, the effect of sulfur was less pronounced on mass transfer/fuel reforming processes but quite significant on the charge transfer/TPB processes. Overall, sulfur related performance loss was more severe at the highest current density (1 A cm−2), due to the deactivation of catalytic fuel reforming reactions......A Ni/ScYSZ based SOFC was tested at 1, 0.5, 0.25, and 0 (OCV) A cm−2 in methane fuel containing 0–100 ppm H2S. Analysis of cell voltage loss during short-term H2S poisoning showed that SOFC performance loss was generally larger at higher current loads. Separating the effect of H2S on catalytic...... reforming and electrochemical activity by evaluating the relevant area specific resistances and charge transfer processes based on impedance spectroscopy revealed that the poisoning of electrochemical activity was not dependent on current density. Two major anode processes were significantly affected...

Additive effect of Ce, Mo and K to nickel-cobalt aluminate supported solid oxide fuel cell for direct internal reforming of methane

Energy Technology Data Exchange (ETDEWEB)

Kwak, Bu Ho; Park, Jungdeok; Yoon, Heechul; Kim, Hyeon Hui; Kim, Lim; Chung, Jong Shik [POSTECH, Pohang (Korea, Republic of)

2014-01-15

Direct internal reforming of methane (steam/carbon=0.031, 850 .deg. C) is tested using button cells of Ni-YSZ/YSZ/LSM in which the anode layer is supported either on Ni-YSZ or on Ni-CoAl{sub 2}O{sub 4}. The Ni-CoAl{sub 2}O{sub 4} supported cell shows little degradation with operating time, as a result of higher resistance against carbon deposition, whereas the Ni-YSZ supported cell deactivates quickly and suffers fracture in 50 h. Upon incorporation of additives such as K, Ce, or Mo into the Ni-CoAl{sub 2}O{sub 4} support, cells with 0.5 wt% CeO{sub 2} exhibit the best stable performance as a result of reduced coke formation. Cells with 0.5 wt% Mo exhibit the lowest performance. Although no carbon deposit is detected in the cells with K{sub 2}CO{sub 3} additives, their performance is worse than that in the CeO{sub 2} case, and, in constant-current mode, there is a sudden voltage drop to zero after a certain period of time; this time becomes shorter with increasing K content. The injection of potassium into the anode side facilitates the generation of OH{sup -} and CO{sub 3}{sup 2-} in the anode and promotes the diffusion of these ions to the cathode. Increased polarization resistance at the cathode and increased electrolyte resistance result in such a sudden failure.

Atmospheric methane removal by methane-oxidizing bacteria immobilized on porous building materials.

Science.gov (United States)

Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Hoefman, Sven; De Vos, Paul; Boeckx, Pascal; Boon, Nico

2014-04-01

Biological treatment using methane-oxidizing bacteria (MOB) immobilized on six porous carrier materials have been used to mitigate methane emission. Experiments were performed with different MOB inoculated in building materials at high (~20 % (v/v)) and low (~100 ppmv) methane mixing ratios. Methylocystis parvus in autoclaved aerated concrete (AAC) exhibited the highest methane removal rate at high (28.5 ± 3.8 μg CH₄ g⁻¹ building material h⁻¹) and low (1.7 ± 0.4 μg CH₄ g⁻¹ building material h⁻¹) methane mixing ratio. Due to the higher volume of pores with diameter >5 μm compared to other materials tested, AAC was able to adsorb more bacteria which might explain for the higher methane removal observed. The total methane and carbon dioxide-carbon in the headspace was decreased for 65.2 ± 10.9 % when M. parvus in Ytong was incubated for 100 h. This study showed that immobilized MOB on building materials could be used to remove methane from the air and also act as carbon sink.

Linseed plus nitrate in the diet for fattening bulls: effects on methane emission, animal health and residues in offal.

Science.gov (United States)

Doreau, M; Arbre, M; Popova, M; Rochette, Y; Martin, C

2018-03-01

The combination of linseed and nitrate is known to decrease enteric methane emission in dairy cows but few studies have been carried out in fattening cattle for animal liveweight gain, enteric methane emission, animal health and presence of residues in beef products. To address this gap, 16 young bulls received a control (C) diet between weaning at 9 months and 14 months, then were split into two groups of eight balanced on feed intake, BW gain and methane emission to receive either the C diet or a diet moderately supplemented with extruded linseed and calcium nitrate (LN) for 2 months before being slaughtered. On a dry matter (DM) basis, the C diet contained 70% baled grass silage and 30% concentrate mainly made of maize, wheat and rapeseed meal. In the LN diet, rapeseed meal and a fraction of cereals were replaced by 35% extruded linseed and 6% calcium nitrate; linseed fatty acids and nitrate supply in the LN diet were 1.9% and 1.0%, respectively. Methane emission was measured continuously using the GreenFeed system. Methaemoglobin was determined every week in peripheral blood from bulls receiving the LN diet. Nitrate and nitrite concentrations were determined in rumen, liver and tongue sampled at slaughter. Dry matter intake tended to be lower for LN diet (P=0.10). Body weight gain was lower for LN diet (P=0.01; 1.60 and 1.26 kg/day for C and LN diet, respectively). Daily methane emission was 9% lower (Pmethane yield did not differ between diets (24.1 and 23.2 g/kg DM intake for C and LN diet, respectively, P=0.34). Methaemoglobin was under the limit of detection (methane yield and impaired bull liveweight gain but without adverse effects for animal health and food safety.

Rain increases methane production and methane oxidation in a boreal thermokarst bog

Science.gov (United States)

Neumann, R. B.; Moorberg, C.; Turner, J.; Wong, A.; Waldrop, M. P.; Euskirchen, E. S.; Edgar, C.; Turetsky, M. R.

2017-12-01

Bottom-up biogeochemical models of wetland methane emissions simulate the response of methane production, oxidation and transport to wetland conditions and environmental forcings. One reason for mismatches between bottom-up and top-down estimates of emissions is incomplete knowledge of factors and processes that control microbial rates and methane transport. To advance mechanistic understanding of wetland methane emissions, we conducted a multi-year field investigation and plant manipulation experiment in a thermokarst bog located near Fairbanks, Alaska. The edge of the bog is experiencing active permafrost thaw, while the center of the bog thawed 50 to 100 years ago. Our study, which captured both an average year and two of the wettest years on record, revealed how rain interacts with vascular vegetation and recently thawed permafrost to affect methane emissions. In the floating bog, rain water warmed and oxygenated the subsurface, but did not alter soil saturation. The warmer peat temperatures increased both microbial methane production and plant productivity at the edge of the bog near the actively thawing margin, but minimally altered microbial and plant activity in the center of the bog. These responses indicate processes at the edge of the bog were temperature limited while those in the center were not. The compounding effect of increased microbial activity and plant productivity at the edge of the bog doubled methane emissions from treatments with vascular vegetation during rainy years. In contrast, methane emissions from vegetated treatments in the center of the bog did not change with rain. The oxygenating influence of rain facilitated greater methane oxidation in treatments without vascular vegetation, which offset warming-induced increases in methane production at the edge of the bog and decreased methane emissions in the center of the bog. These results elucidate the complex and spatially variable response of methane production and oxidation in

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.

A comprehensive energy–exergy-based assessment and parametric study of a hydrogen production process using steam glycerol reforming

International Nuclear Information System (INIS)

Hajjaji, Noureddine; Chahbani, Amna; Khila, Zouhour

2014-01-01

Various assessment tools are applied to comprehensively investigate a glycerol-to-hydrogen production system. These tools investigate the chemical reactions, design and simulate the entire hydrogen production process, study the energetic and exergetic performances and perform parametric analyses (using intuitive and design of experiment-based methods). Investigating the chemical reaction of steam glycerol reforming reveals that the optimal conditions, determined based on maximizing the hydrogen production while minimizing the methane and carbon monoxide contents and coke formation, can be achieved at a reforming temperature and a water-to-glycerol feed ratio (WGFR) of 950 K and 9, respectively. The thermal and exergetic efficiencies of the resulting process are 66.6% and 59.9%, respectively. These findings are lower than those cited in the literature and relative to other reformates (methane, ethanol and methanol). The parametric investigation indicates that the performance of the process (energetic and exergetic) could be ensured by using an appropriate and judiciously selected combination of the reactor temperature and WGFR. Based on the parametric energetic and exergetic investigation, WGFR = 6 and T = 1100 K appear to be the most accurate parameters for the entire glycerol-to-hydrogen process. For this recommend configuration, the thermal and exergetic efficiencies are 78.1% and 66.1%, respectively. - Highlights: • Energy and exergy analysis are used to assess glycerol-to-hydrogen process. • Recommended conditions for glycerol-to-hydrogen process are WGFR = 6 and T = 1100 K. • For recommend conditions, thermal and exergetic efficiencies are 78.1% and 66.1%. • Energy and exergy consideration should be included by engineers and scientists

Evaluation of the Effects of Iron Oxides on Soil Reducing Conditions and Methane Generation in Cambodian Wetland Rice Fields

Science.gov (United States)

Weaver, M.; Benner, S.; Fendorf, S.; Sampson, M.; Leng, M.

2007-12-01

Atmospheric concentrations of methane have been steadily increasing over the last 100 years, which has given rise to research of wetland rice fields, recently identified as a major anthropomorphic source of methane. Establishment of experimental soil pots, cultivating an aromatic early variety rice strain in the Kean Svay District of Cambodia, have recently been carried out to evaluate methods to minimize methane release by promoting redox buffering by iron oxides. In the first series of experiments, iron oxides were added to the soils and the rate of change in reducing conditions and methanogenesis onset was monitored. In the second series of experiments, plots are subject to periodic drying cycles to promote rejuvenation of buffering iron oxides. Initial results indicate a delay in the onset of methanogenesis, and overall methane generation, in plots where initial iron oxides concentrations are elevated.

High Efficiency Solar-based Catalytic Structure for CO₂ Reforming

Energy Technology Data Exchange (ETDEWEB)

Menkara, Hisham [PhosphorTech Corporation, Kennesaw, GA (United States)

2013-09-30

Throughout this project, we developed and optimized various photocatalyst structures for CO₂ reforming into hydrocarbon fuels and various commodity chemical products. We also built several closed-loop and continuous fixed-bed photocatalytic reactor system prototypes for a larger-scale demonstration of CO₂ reforming into hydrocarbons, mainly methane and formic acid. The results achieved have indicated that with each type of reactor and structure, high reforming yields can be obtained by refining the structural and operational conditions of the reactor, as well as by using various sacrificial agents (hole scavengers). We have also demonstrated, for the first time, that an aqueous solution containing acid whey (a common bio waste) is a highly effective hole scavenger for a solar-based photocatalytic reactor system and can help reform CO₂ into several products at once. The optimization tasks performed throughout the project have resulted in efficiency increase in our conventional reactors from an initial 0.02% to about 0.25%, which is 10X higher than our original project goal. When acid whey was used as a sacrificial agent, the achieved energy efficiency for formic acid alone was ~0.4%, which is 16X that of our original project goal and higher than anything ever reported for a solar-based photocatalytic reactor. Therefore, by carefully selecting sacrificial agents, it should be possible to reach energy efficiency in the range of the photosynthetic efficiency of typical crop and biofuel plants (1-3%).

Reactor modeling of sorption-enhanced autothermal reforming of methane. Part I: Performance study of hydrotalcite and lithium zirconate-based processes

NARCIS (Netherlands)

Halabi, M.H.; Croon, de M.H.J.M.; Schaaf, van der J.; Cobden, P.D.; Schouten, J.C.

2011-01-01

This paper presents a performance analysis for the sorption-enhanced autothermal reforming of CH4 in a fixed bed reformer for pure H2 production with in situ CO2 capture. The process is analyzed for two candidate sorbents of K-promoted hydrotalcite and lithium zirconate in a fixed bed reactor using

Rapid solar-thermal decarbonization of methane

Science.gov (United States)

Dahl, Jaimee Kristen

Due to the ever-increasing demand for energy and the concern over the environmental impact of continuing to produce energy using current methods, there is interest in developing a hydrogen economy. Hydrogen is a desirable energy source because it is abundant in nature and burns cleanly. One method for producing hydrogen is to utilize a renewable energy source to obtain high enough temperatures to decompose a fossil fuel into its elements. This thesis work is directed at developing a solar-thermal aerosol flow reactor to dissociate methane to carbon black and hydrogen. The technology is intended as a "bridge" between current hydrogen production methods, such as conventional steam-methane reformers, and future "zero emission" technology for producing hydrogen, such as dissociating water using a renewable heating source. A solar furnace is used to heat a reactor to temperatures in excess of 2000 K. The final reactor design studied consists of three concentric vertical tubes---an outer quartz protection tube, a middle solid graphite heating tube, and an inner porous graphite reaction tube. A "fluid-wall" is created on the inside wall of the porous reaction tube in order to prevent deposition of the carbon black co-product on the reactor tube wall. The amorphous carbon black produced aids in heating the gas stream by absorbing radiation from the reactor wall. Conversions of 90% are obtained at a reactor wall temperature of 2100 K and an average residence time of 0.01 s. Computer modeling is also performed to study the gas flow and temperature profiles in the reactor as well as the kinetics of the methane dissociation reaction. The simulations indicate that there is little flow of the fluid-wall gas through the porous wall in the hot zone region, but this can be remedied by increasing the inlet temperature of the fluid-wall gas and/or increasing the tube permeability only in the hot zone region of the wall. The following expression describes the kinetics of methane

Hydrogen Production by Steam Reforming of Liquefied Natural Gas (LNG) Over Nickel-Phosphorus-Alumina Xerogel Catalyst Prepared by a Carbon-Templating Epoxide-Driven Sol-Gel Method.

Science.gov (United States)

Bang, Yongju; Park, Seungwon; Han, Seung Ju; Yoo, Jaekyeong; Choi, Jung Ho; Kang, Tae Hun; Lee, Jinwon; Song, In Kyu

2016-05-01

A nickel-phosphorus-alumina xerogel catalyst was prepared by a carbon-templating epoxide-driven sol-gel method (denoted as CNPA catalyst), and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel-phosphorus-alumina xerogel catalyst was also prepared by a similar method in the absence of carbon template (denoted as NPA catalyst). The effect of carbon template addition on the physicochemical properties and catalytic activities of the catalysts in the steam reforming of LNG was investigated. Both CNPA and NPA catalysts showed excellent textural properties with well-developed mesoporous structure. However, CNPA catalyst retained a more reducible nickel aluminate phase than NPA catalyst. XRD analysis of the reduced CNPA and NPA catalysts revealed that nickel sintering on the CNPA catalyst was suppressed compared to that on the NPA catalyst. From H2-TPD and CH4-TPD measurements of the reduced CNPA and NPA catalysts, it was also revealed that CNPA catalyst with large amount of hydrogen uptake and strong hydrogen-binding sites showed larger amount of methane adsorption than NPA catalyst. In the hydrogen production by steam reforming of LNG, CNPA catalyst with large methane adsorption capacity showed a better catalytic activity than NPA catalyst.

Catalytic activity of catalysts for steam reforming reaction. Contract research

Energy Technology Data Exchange (ETDEWEB)

Ohashi, Hirofumi; Inagaki, Yoshiyuki [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment

2003-05-01

Japan Atomic Energy Research Institute has been developing a hydrogen production system by means of steam reforming of methane (chemical reation: CH{sub 4} + H{sub 2}O = CO + 3H{sub 2}) coupling with High Temperature Engineering Test Reactor (HTTR) to demonstrate effectiveness of high-temperature nuclear heat utilization. Prior to construction of HTTR hydrogen production system, a mock-up test facility with a full-scale reaction tube was constructed to investigate transient behavior of the hydrogen production system an establish system controllability. In order to predict transient behavior and hydrogen productivity of the hydrogen production system, it is important to estimate the reaction characteristics under the same temperature and pressure conditions as those of HTTR hydrogen production system. For the purpose of investigate an apparent activation energy of catalysts, catalytic activity test using small apparatus was carried out under the condition of methane flow rate from 1.18 x 10{sup -3} to 3.19 x 10{sup -3} mol/s, temperature from 500 to 900degC, pressure from 1.1 to 4.1MPa, and mol ratio of steam to methane from 2.5 to 3.5. It was confirmed that apparent activation energies of two kinds of Ni catalysts which are to be used in the mock-up test were 51.7 and 57.4kJ/mol, respectively, and reaction rate constants were propositional to the value from P{sup -0.15} to P{sup -0.33}. (author)

75 FR 67607 - Dried Prunes Produced in California; Increased Assessment Rate

Science.gov (United States)

2010-11-03

... Order 12988, Civil Justice Reform. Under the marketing order now in effect, California dried prune... DEPARTMENT OF AGRICULTURE Agricultural Marketing Service 7 CFR Part 993 [Doc. No. AMS-FV-10-0057... Marketing Service, USDA. ACTION: Final rule. SUMMARY: This rule increases the assessment rate established...

Development of a coupled reactor with a catalytic combustor and steam reformer for a 5 kW solid oxide fuel cell system

International Nuclear Information System (INIS)

Kang, Sanggyu; Lee, Kanghun; Yu, Sangseok; Lee, Sang Min; Ahn, Kook-Young

2014-01-01

Highlights: • Proposes the scale-up strategy to develop a large-scale coupled reactor. • Investigation of performance of steam reformer coupled with catalytic combustor. • Experimental parameters are inlet temp., air excess ratio, SCR, fuel utilization. • Evaluation of the heat transfer distribution along the gas flow direction. • The mean value of methane conversion rate is approximately 93.4%. - Abstract: The methane (CH 4 ) conversion rate of a steam reformer can be increased by thermal integration with a catalytic combustor, called a coupled reactor. In the present study, a 5 kW coupled reactor has been developed based on a 1 kW coupled reactor in previous work. The geometric parameters of the space velocity, diameter and length of the coupled reactor selected from the 1 kW coupled reactor are tuned and applied to the design of the 5 kW coupled reactor. To confirm the scale-up strategy, the performance of 5 kW coupled reactor is experimentally investigated with variations of operating parameters such as the fuel utilization in the solid oxide fuel cell (SOFC) stack, the inlet temperature of the catalytic combustor, the excess air ratio of the catalytic combustor, and the steam to carbon ratio (SCR) in the steam reformer. The temperature distributions of coupled reactors are measured along the gas flow direction. The gas composition at the steam reformer outlet is measured to find the CH 4 conversion rate of the coupled reactor. The maximum value of the CH 4 conversion rate is approximately 93.4%, which means the proposed scale-up strategy can be utilized to develop a large-scale coupled reactor

Modelling of plasma-based dry reforming: how do uncertainties in the input data affect the calculation results?

Science.gov (United States)

Wang, Weizong; Berthelot, Antonin; Zhang, Quanzhi; Bogaerts, Annemie

2018-05-01

One of the main issues in plasma chemistry modeling is that the cross sections and rate coefficients are subject to uncertainties, which yields uncertainties in the modeling results and hence hinders the predictive capabilities. In this paper, we reveal the impact of these uncertainties on the model predictions of plasma-based dry reforming in a dielectric barrier discharge. For this purpose, we performed a detailed uncertainty analysis and sensitivity study. 2000 different combinations of rate coefficients, based on the uncertainty from a log-normal distribution, are used to predict the uncertainties in the model output. The uncertainties in the electron density and electron temperature are around 11% and 8% at the maximum of the power deposition for a 70% confidence level. Still, this can have a major effect on the electron impact rates and hence on the calculated conversions of CO2 and CH4, as well as on the selectivities of CO and H2. For the CO2 and CH4 conversion, we obtain uncertainties of 24% and 33%, respectively. For the CO and H2 selectivity, the corresponding uncertainties are 28% and 14%, respectively. We also identify which reactions contribute most to the uncertainty in the model predictions. In order to improve the accuracy and reliability of plasma chemistry models, we recommend using only verified rate coefficients, and we point out the need for dedicated verification experiments.

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.

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)

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

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