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.

Sulphur poisoning of palladium catalysts used for methane combustion: Effect of the support

International Nuclear Information System (INIS)

Escandon, Lara S.; Ordonez, Salvador; Vega, Aurelio; Diez, Fernando V.

2008-01-01

Four different supported palladium catalysts (using alumina, silica, zirconia and titania as supports), prepared by incipient wetness impregnation, were tested as catalysts for methane oxidation in presence of sulphur dioxide. The catalyst supported on zirconia showed the best performance, whereas the silica-supported one showed the fastest deactivation. Temperature-programmed desorption experiments of the poisoned catalysts suggest that SO 2 adsorption capacity of the support plays a key role in the catalyst poisoning. In order to study the effect of promoters, expected to improve the thermal stability and thioresistance of the catalyst, commercial zirconia modified by yttrium and lantane was tested as supports. It was found that the presence of these promoters does not improve the performance of the zirconia-supported catalyst. A deactivation model - considering two different active sites (fresh and poisoning), pseudo-first order dependence on methane concentration and poisoning rate depending on sulphur concentration and fraction of non-poisoned palladium - was used for modelling the deactivation behaviour

Report on a survey in fiscal 1999. Direct oxidation of hydrocarbons by manifestation of functions of methane mono-oxygenase (MMO); 1999 nendo metamonookishinaze (MMO) no kino hatsugen ni yoru tanka suiso no chokusetsu sanka seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

The metallic enzyme, methane mono-oxygenase (MMO) collected from methanotrophic bacteria, may perform a reaction that has a possibility to proceed direct conversion from methane to methanol under normal temperatures and pressures. However, its utilization of biological bacteria makes massive cultivation and handling difficult, not having realized its practical use. Therefore, research and development has been carried out on a process that can convert directly and selectively hydrocarbons including methane under normal temperatures and pressures, mimicking the excellent functions of MMO. To achieve the development, surveys and discussions were given on the following elementary researches: elucidation of the reaction mechanism in the activation point in microorganism enzymes; analysis of structures in microorganism MMO; creation of a technology to develop a bio-mimetic catalyst; improvement in selectivity of the bio-mimetic catalyst; and international joint research (basic analysis of the catalyst mechanism). As a result, technological problems in developing the mimetic catalyst were put into order, and guidelines and measures for specific catalyst designing are being proposed. Furthermore, a way was opened for international joint research with the complex synthesis research group in CNRS in France, and progress into the step of demonstrating and discussing the feasibility thereof is now ready. (NEDO)

The Carbonation of Wollastonite: A Model Reaction to Test Natural and Biomimetic Catalysts for Enhanced CO2 Sequestration

Directory of Open Access Journals (Sweden)

Fulvio Di Lorenzo

2018-05-01

Full Text Available One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO2 capture and storage (CCS. Here, we studied the different steps of wollastonite (CaSiO3 carbonation (silicate dissolution → carbonate precipitation as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA, a natural enzyme that catalyzes the reversible hydration of CO2(aq, and biomimetic metal-organic frameworks (MOFs. Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl-specific. CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS.

Facile one-pot synthesis of porphyrin based porous polymer networks (PPNs) as biomimetic catalysts

Energy Technology Data Exchange (ETDEWEB)

Zou, LF; Feng, DW; Liu, TF; Chen, YP; Fordham, S; Yuan, S; Tian, J; Zhou, HC

2015-01-01

Stable porphyrin based porous polymer networks, PPN-23 and PPN-24, have been synthesized through a facile one-pot approach by the aromatic substitution reactions of pyrrole and aldehydes. PPN-24(Fe) shows high catalytic efficiency as a biomimetic catalyst in the oxidation reaction of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) in the presence of H2O2.

Exquisite Enzyme-Fenton Biomimetic Catalysts for Hydroxyl Radical Production by Mimicking an Enzyme Cascade.

Science.gov (United States)

Zhang, Qi; Chen, Shuo; Wang, Hua; Yu, Hongtao

2018-03-14

Hydrogen peroxide (H 2 O 2 ) is a key reactant in the Fenton process. As a byproduct of enzymatic reaction, H 2 O 2 can be obtained via catalytical oxidation of glucose using glucose oxidase in the presence of O 2 . Another oxidation product (gluconic acid) can suitably adjust the microenvironmental pH contributing to the Fe 3+ /Fe 2+ cycle in the Fenton reaction. Enzymes are extremely efficient at catalyzing a variety of reactions with high catalytic activity, substrate specificity, and yields in living organisms. Inspired by the multiple functions of natural multienzyme systems, an exquisite nanozyme-modified α-FeOOH/porous carbon (PC) biomimetic catalyst constructed by in situ growth of glucose oxidase-mimicking Au nanoparticles and crystallization of adsorbed ferric ions within carboxyl into hierarchically PC is developed as an efficient enzyme-Fenton catalyst. The products (H 2 O 2 , ∼4.07 mmol·L -1 ) of the first enzymatic reaction are immediately used as substrates for the second Fenton-like reaction to generate the valuable • OH (∼96.84 μmol·L -1 ), thus mimicking an enzyme cascade pathway. α-FeOOH nanocrystals, attached by C-O-Fe bondings, are encapsulated into the mesoporous PC frameworks, facilitating the electron transfer between α-FeOOH and the PC support and greatly suppressing iron leaching. This study paves a new avenue for designing biomimetic enzyme-based Fenton catalysts mimicking a natural system for • OH production.

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

Science.gov (United States)

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

2018-02-01

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

Influence of zeolite structure on the activity and durability of Co-Pd-zeolite catalysts in the reduction of NOx with methane

International Nuclear Information System (INIS)

Pieterse, J.A.Z.; Van den Brink, R.W.; Booneveld, S.; De Bruijn, F.A.

2003-01-01

Selective catalytic reduction of NO with CH 4 was studied over ZSM-5, MOR, FER and BEA zeolite-based cobalt (Co) and palladium (Pd) catalysts in the presence of oxygen and water. As compared to other catalytic systems reported in literature for CH 4 -SCR in the presence of water, zeolite supported Co-Pd combination catalysts are very active and selective. The most active catalysts, based on MOR and ZSM-5, are characterised by well-dispersed Pd ions in the zeolite that activate methane. Wet ion exchange is a good method to achieve high dispersion of Pd provided that it is carried out in a competitive manner. The presence of cobalt (Co 3 O 4 , Co-oxo ions) boosts SCR activity by oxidising NO to NO 2 . The activity of the zeolite-based Co-Pd combination catalysts decreases with prolonged times on stream. The severity of the deactivation was found to be different for different zeolite topologies. The characterisation and evaluation of freshly calcined catalysts and spent catalysts show two things that occur during reaction: (1) zeolite solvated metal cations disappear in favour of (inactive) metal oxides and presumably larger metal entities, i.e. loss of dispersion; (2) loss of crystallinity affiliated with steam-dealumination and the concomitant formation of extra-framework aluminium (EFAL) in the presence of water. Both phenomena strongly depend on the (reaction) temperature. The deactivation of Co-Pd-zeolite resembles the deactivation of Pd-zeolite. Hence, future research could encompass the stabilisation of Pd (cations) in the zeolite pores by exploring additives other than cobalt. For this, detailed understanding on the siting of Pd in zeolites is important

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...

Formaldehyde formation in coupled oxidation of methane and methanol over V2O5 and MoO3 silica supported catalysts

International Nuclear Information System (INIS)

Lojewska, J.; Makowski, W.; Fajardo Farre, A.; Dziembaj, R.

2003-01-01

The effect of methanol on partial oxidation of methane has been studied on standard molybdena and vanadia catalysts supported on silica. Prior to catalytic tests the catalysts were characterized by BET, SEM/EDAX and TPR/O methods. Three types of catalytic tests were performed giving temperature and contact time dependence on the catalyst activity and selectivity: partial oxidations of methane, methanol and methane/methanol mixtures. The methanol showed an activating impact on the partial oxidation of methane over all used catalysts samples, but the strongest one over Mo 3 /SiO 2 . In the absence of CH 3 OH the only catalyst, which exhibited HCHO selectivity, was low loaded vanadia catalyst. It has been put forward that methanol may enhance formation of oxygen active species, prerequisites for activating methane molecules, through reducing vanadia cations and causing breakage of vanadium oxygen bonds. (author)

Methane oxidation over noble metal catalysts as related to controlling natural gas vehicle exhaust emissions

International Nuclear Information System (INIS)

Oh, S.H.; Mitchell, P.J.; Siewert, R.M.

1992-01-01

Natural gas has considerable potential as an alternative automotive fuel. This paper reports on methane, the principal hydrocarbon species in natural-gas engine exhaust, which has extremely low photochemical reactivity but is a powerful greenhouse gas. Therefore, exhaust emissions of unburned methane from natural-gas vehicles are of particular concern. This laboratory reactor study evaluates noble metal catalysts for their potential in the catalytic removal of methane from natural-gas vehicle exhaust. Temperature run-up experiments show that the methane oxidation activity decreases in the order Pd/Al 2 O 3 > Rh/Al 2 O 3 > Pt/Al 2 O 3 . Also, for all the noble metal catalysts studied, methane conversion can be maximized by controlling the O 2 concentration of the feedstream at a point somewhat rich (reducing) of stoichiometry

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 ...

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

International Nuclear Information System (INIS)

Lopez U, A. C.

2016-01-01

The main objective of this thesis is development of nickel catalysts supported over 1D matrix of cerium oxide, to be used in dry reforming methane reaction with carbon dioxide for hydrogen production. The catalysts were characterized by: Temperature Programmed Reduction (TPR), Scanning Electronic Microscopy (Sem), Surface Area (Bet method) an X Ray Diffraction (XRD). The TPR technique allowed to define reduction temperature of the active phase in the catalyst, Sem technique showed that the CeO_2 matrix had a nano rod morphology. XRD allowed to identify the crystalline phases of the catalysts. Finally, the catalysts were tested in the dry reforming methane reaction, high catalytic activity and hydrogen production were performed at 700 degrees Celsius and the catalyst with 30 wt.% of nickel. (Author)

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

KAUST Repository

Zhou, Lu

2017-09-08

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

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

KAUST Repository

Zhou, Lu; Harb, Moussab; Enakonda, Linga Reddy; Al Mana, Noor; Hedhili, Mohamed N.; Basset, Jean-Marie

2017-01-01

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

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.

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

Directory of Open Access Journals (Sweden)

Mirda Yanti Fusia

2017-01-01

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

METHANE STEAM REACTION OVER NICKEL CATALYSTS IN THE HYNOL PROCESS

Science.gov (United States)

The report discusses the reaction of methane-steam over nickel catalysts in the Hynol process, a process that uses biomass and natural gas as feedstocks to maximize methanol yields and minimize greenhouse gas emissions. EPA's APPCD has established a laboratory in which to conduct...

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

Directory of Open Access Journals (Sweden)

Hyun Ook Seo

2018-03-01

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

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.

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)

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

Jacobsen Catalyst as a Cytochrome P450 Biomimetic Model for the Metabolism of Monensin A

Directory of Open Access Journals (Sweden)

Bruno Alves Rocha

2014-01-01

Full Text Available Monensin A is a commercially important natural product isolated from Streptomyces cinnamonensins that is primarily employed to treat coccidiosis. Monensin A selectively complexes and transports sodium cations across lipid membranes and displays a variety of biological properties. In this study, we evaluated the Jacobsen catalyst as a cytochrome P450 biomimetic model to investigate the oxidation of monensin A. Mass spectrometry analysis of the products from these model systems revealed the formation of two products: 3-O-demethyl monensin A and 12-hydroxy monensin A, which are the same ones found in in vivo models. Monensin A and products obtained in biomimetic model were tested in a mitochondrial toxicity model assessment and an antimicrobial bioassay against Staphylococcus aureus, S. aureus methicillin-resistant, Staphylococcus epidermidis, Pseudomonas aeruginosa, and Escherichia coli. Our results demonstrated the toxicological effects of monensin A in isolated rat liver mitochondria but not its products, showing that the metabolism of monensin A is a detoxification metabolism. In addition, the antimicrobial bioassay showed that monensin A and its products possessed activity against Gram-positive microorganisms but not for Gram-negative microorganisms. The results revealed the potential of application of this biomimetic chemical model in the synthesis of drug metabolites, providing metabolites for biological tests and other purposes.

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

Energy Technology Data Exchange (ETDEWEB)

McCormick, R.L.

1997-10-01

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

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...

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

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)

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

Energy Technology Data Exchange (ETDEWEB)

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

2004-07-01

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

Engineered Sulfur‐Resistant Catalyst System with an Assisted Regeneration Strategy for Lean‐Burn Methane Combustion

Science.gov (United States)

Kallinen, Kauko; Maunula, Teuvo; Suvanto, Mika

2018-01-01

Abstract Catalytic combustion of methane, the main component of natural gas, is a challenge under lean‐burn conditions and at low temperatures owing to sulfur poisoning of the Pd‐rich catalyst. This paper introduces a more sulfur‐resistant catalyst system that can be regenerated during operation. The developed catalyst system lowers the barrier that has restrained the use of liquefied natural gas as a fuel in energy production. PMID:29780434

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-06-15

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

Pd enhanced WC catalyst to promote heterogeneous methane combustion

International Nuclear Information System (INIS)

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

2017-01-01

Highlights: • Pd enhanced WC catalyst particles were synthesized via mechanochemical alloying. • Catalyst was characterized by XRD, XRF, SEM, and EDS. • Catalyst was deposited on porous ZrO_2 and evaluated in heterogeneous combustion. • During combustion temperature profiles and spectral emissions were collected. - Abstract: The efficiency of combustion for low cost heat production could be greatly enhanced if an active and low cost catalyst would be used to facilitate the chemical reactions occurring during combustor operation. Within this work an experimental study of palladium (Pd) enhanced tungsten carbide (WC) catalyst, synthesized via high energy ball milling and deposited by dip coating onto a magnesia partially stabilized zirconia (MgO-ZrO_2) porous matrix of 10 ppin was evaluated in heterogeneous methane combustion. The synthesized powder was characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) coupled with Energy Dispersive Spectroscopy (EDS) analysis, as well as by X-ray Fluorescence (XRF); and the morphology of the deposited WC-Pd coating was also characterized using SEM and EDS. Performance evaluation of the heterogeneous combustor with WC-Pd coated MgO-ZrO_2 porous media was conducted at constant air flow rate and various equivalence ratios of methane/air gaseous mixtures, while monitoring axial temperature profiles within the combustion chamber using thermocouples, as well as thermal radiative and acoustic emissions from the combustor exhaust using an externally placed CCD camera and a microphone. It was found that there is a strong dependence of flame position and maximum temperature on equivalence ratio (φ) over the range of 0.47 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02. Additionally it was found that over the same equivalence ratio range, there is a characteristic 4 peak acoustic signature between 200 and 500 Hz. It was found that at higher equivalence ratios 0.51 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02 the performance of combustor

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

KAUST Repository

Zhou, Lu

2018-03-27

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-09-15

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

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.

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

KAUST Repository

Li, Lidong

2015-01-08

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

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

Directory of Open Access Journals (Sweden)

R.Y. Raskar

2012-06-01

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

Nitrogen as a regulatory factor of methane oxidation in soils and sediments

NARCIS (Netherlands)

Bodelier, P.L.E.; Laanbroek, H.J.

2004-01-01

The oxidation of methane by methane-oxidising microorganisms is an important link in the global methane budget. Oxic soils are a net sink while wetland soils are a net source of atmospheric methane. It has generally been accepted that the consumption of methane in upland as well as lowland systems

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

Hydrogen or synthesis gas production via the partial oxidation of methane over supported nickel-cobalt catalysts

Energy Technology Data Exchange (ETDEWEB)

Koh, Alaric C.W. [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Chen, Luwei; Lin, Jianyi [Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Kee Leong, Weng [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Johnson, Brian F.G.; Khimyak, Tetyana [University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW (United Kingdom)

2007-05-15

Activity, selectivity, and coking-resistance of a series of Ni{sub x}Co{sub y} (where x,y are the respective metal loadings of 0, 1, 2 or 3 wt.%; x+y=3) bimetallic catalysts supported on CaAl{sub 2}O{sub 4}/Al{sub 2}O{sub 3} have been studied for hydrogen/synthesis gas production via the catalytic partial oxidation (CPO) of methane. Catalysts were characterized by temperature programmed reduction (TPR), transmission electron microscopy (TEM) and X-ray fluorescence multi-element analysis (XRF). Their activity for the partial oxidation of methane to hydrogen and carbon monoxide (at 1 bar, gas hourly space velocity (GHSV) of 144,000cm{sup 3}g{sup -1}h{sup -1} and CH{sub 4}/O{sub 2} molar ratio of 2) was investigated, and coke deposited on the spent catalysts was studied by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA). The activity was found to decrease in the order of Ni{sub 2}Co>Ni{sub 3}>NiCo{sub 2}>>Co{sub 3}, while CO and H{sub 2} selectivities were found to be in the order ofNi{sub 2}Co>Ni{sub 3}{approx}NiCo{sub 2}>Co{sub 3}. Ni{sub 2}Co is also shown to be more resistant to coking as compared to Ni{sub 3}, which is a current catalyst of choice. Results show that not only does Ni{sub 2}Co have the highest activity and selectivity among all the catalysts tested, it is also relatively resistant to coking. This finding would be helpful for catalyst design to achieve high coking resistivity catalysts for hydrogen production from CPO of methane. (author)

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

Science.gov (United States)

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

2017-08-01

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

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

Directory of Open Access Journals (Sweden)

A.S. Al-Fatesh

2018-02-01

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

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

NARCIS (Netherlands)

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

1987-01-01

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

Catalytic oxidation of concentrated orange oil phase by synthetic metallic complexes biomimetic to MMO enzyme.

Science.gov (United States)

Fernandes, Ilizandra A; Esmelindro, Maria Carolina; Corazza, Marcos L; Franceschi, Elton; Treichel, Helen; de Oliveira, Debora; Frizzo, Caren D; Oliveira, J Vladimir

2010-07-01

This paper reports the catalytic oxidation of the concentrated orange oil phase using the complexes [Fe(III)(BMPP)Cl(micro-O)Fe(III)Cl(3)], [Cu(II)(BTMEA)(2)Cl]Cl and [Co(II)(BMPP)]Cl(2) biomimetic to methane monooxygenase enzyme as catalysts and hydrogen peroxide as oxidant. The reaction products of oil oxidation, mainly nootkatone, were identified by gas chromatography/mass spectrometry. A screening of catalysts was performed through a full 2(3) experimental design, varying the temperature from 30 to 70 degrees C, the catalyst concentration from 7.0 x 10(-4) to 1.5 x 10(-3) mol L(-1) and the oxidant/substrate molar ratio from 1:1 to 3:1. The results of reaction kinetics employing the most promising catalysts showed that conversions to nootkatone of up to 8% were achieved after 16 h at 70 degrees C. The results obtained in this study in terms of nootkatone production should be considered encouraging, since a real, industrially collected, raw material, instead of pure valencene, was employed in the reaction experiments, with a final content about ten times that present in the original concentrated oil.

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

International Nuclear Information System (INIS)

Wang Kangjun; Li Xiaosong; Zhu Aimin

2011-01-01

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

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-09-26

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-01

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

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

NARCIS (Netherlands)

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

1992-01-01

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

CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

Science.gov (United States)

Wang, Xiaoliu; Zhu, Lingjun; Liu, Yincong; Wang, Shurong

2018-06-01

CO 2 as a raw feed combined with renewable hydrogen for the production of useful chemicals and alternative energy products is one of the solutions to environmental and energy problems. In this study, a series of Ni-xCeO 2 /MCM-41 catalysts with a nickel content of 20wt% were prepared through deposition precipitation method for CO 2 methanation. Different characterization methods, including BET, XRD, TEM, SEM, H 2 -TPR and H 2 -TPD were applied to help explore the influence mechanism of CeO 2 on Ni/MCM-41 in CO 2 methanation. It was found that all CeO 2 -promoted catalysts exhibited enhanced catalytic activity when compared to Ni/MCM-41. The catalyst modified with 20wt% CeO 2 showed the best catalytic performance, with CO 2 conversion and CH 4 selectivity of 85.6% and 99.8%, respectively, at the temperature of 380°C under atmospheric pressure. The synergetic effects among Ni 0 active sites, the promoter and the support, including nickel dispersion improvement and increased CO 2 adsorption sites due to the addition of CeO 2 , were considered as important factors for high reactivity of the promoted catalysts. The stability test showed that the promoted catalyst maintained its high reactivity after 30h. Copyright © 2017 Elsevier B.V. All rights reserved.

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

KAUST Repository

Zhou, Lu; Enakonda, Linga Reddy; Harb, Moussab; Saih, Youssef; Aguilar Tapia, Antonio; Ould-Chikh, Samy; Hazemann, Jean-louis; Li, Jun; Wei, Nini; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

2017-01-01

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

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

KAUST Repository

Zhou, Lu

2017-02-21

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

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 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.

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.

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.

Ventilation air methane destruction - the new challenge to the underground coal mining industry

International Nuclear Information System (INIS)

Clarke, Michael; Seddon, Duncan

2012-01-01

With the advent of 'Carbon Taxes' the carbon footprint of coal has become an economic as well as an environmental issue and the emission of methane in mine out- bye air as ventilation air methane (VAM) is a pending liability. As well as being economic and environmental concerns, VAM and VAM management have safety, social licence and operational factors that must also be addressed. The need to mitigate (oxidise) methane to produce carbon dioxide and water vapour (VAM destruction) and thus lower the Greenhouse footprint is coming to be seen as a necessary mining activity. However, there are several key issues to be addressed with present technology using high temperature (1000°C) thermal oxidisers. Emerging technology may involve a catalytic approach. This technology aims to lower the oxidation temperature and produce a more efficient combustion process. Several systems (based on both precious metals and transition metals) have been shown to operate below 400°C. An ultimate solution would be oxidation at ambient temperature, which is clearly demonstrated by the enzyme methane mono-oxygenase (MMO) which oxidises methane to methanol. However, the rate of oxidation at ambient temperature is too low and the structure of the bio-reactors required would be very large. The challenge is to marry the natural oxidation with modern catalytic approaches and achieve high rates of methane oxidation, in compact equipment, well below the methane auto-ignition temperature.

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

Science.gov (United States)

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

2018-03-01

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

Reaction of methane with coal

Energy Technology Data Exchange (ETDEWEB)

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

1997-10-01

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

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

Directory of Open Access Journals (Sweden)

Yuni Krisyuningsih Krisnandi

2015-11-01

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

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

KAUST Repository

Liang, Yin

2014-03-24

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

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

KAUST Repository

Li, Lidong; Anjum, Dalaver; Zhu, Haibo; Saih, Youssef; Laveille, Paco; D'Souza, Lawrence; Basset, Jean-Marie

2015-01-01

A new dry reforming of methane catalyst comprised of NiCo bimetallic nanoparticles and a Mgx(Al)O support that exhibits high coke resistance and long-term on-stream stability is reported. The structural characterization by XRD, TEM, temperature

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.

Mechanistic insights into heterogeneous methane activation

International Nuclear Information System (INIS)

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

2017-01-01

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

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.

A mechanistic study on the oxidative coupling of methane over lithium doped magnesium oxide catalysts

NARCIS (Netherlands)

Geerts, J.W.M.H.; Kasteren, van J.M.N.; Wiele, van der K.; Imarisio, G.; Frias, M.; Berntgen, J.M.

1988-01-01

To elucidate the importance of various reaction steps in the oxidative convers ion of methane, experiments were carried out with three reaction products: ethane, ethylene and carbon monoxide. These products were studied seperately, in oxidation experiments with and without a catalyst. Moreover , the

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

Directory of Open Access Journals (Sweden)

Wan Azelee Wan Abu Bakar

2015-09-01

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

Electrocatalytic oxidation of methane: investigations of new catalysts to be used in a solid polymer electrolyte methane fuel-cell; Oxydation electrocatalytique du methane: recherche de catalyseurs en vue d'une application a une pile au methane a electrolyte polymere solide

Energy Technology Data Exchange (ETDEWEB)

Berthelot, S

1998-07-01

This thesis evaluated the performances of many catalysts facing the methane oxidation which is a critical step in methane fuel cells development. In a first part the study of the methane electro-oxidation has been realized by classical electrochemical technics on many electrodes to determine the most active ones. In a second part the in situ reflection infra-red spectroscopy allowed to identify, during the methane oxidation, the adsorbed species on the electrode and the reaction products. These results also help the understanding of the part of the concerned materials mechanisms in the methane oxidation and then to optimize them for a whole oxidation of the methane in carbon dioxide. The final objective is the use of the methane in a PEMFC fuel cell type. A comparison with the methanol and C2 hydrocarbons behaviour, such as the ethane the ethylene and the acetylene, has been done to evaluate the performances. (A.L.B.)

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

Czech Academy of Sciences Publication Activity Database

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

2011-01-01

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

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

KAUST Repository

Zhou, Lu

2016-05-18

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

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...

Ruthenium-platinum bimetallic catalysts supported on silica: characterization and study of benzene hydrogenation and CO methanation

Energy Technology Data Exchange (ETDEWEB)

Chakrabarty, D.K.; Rao, K.M.; Sundararaman, N.; Chandavar, K.

1986-12-15

Ru-Pt/SiO/sub 2/ bimetallic catalysts with varying Ru:Pt ratio have been prepared and studied with the aim to establish if they contain coclusters or isolated ruthenium and platinum particles. X-ray diffraction studies show that individual crystallites of ruthenium and platinum are present and no coclusters are formed. Metal dispersion has been determined by hydrogen chemisorption and surface composition of the catalysts has been obtained from XPS. It was found that preoxidation of the catalysts prior to reduction is essential for good platinum dispersion. The experimental turnover number (TN) for benzene hydrogenation on the bimetallic catalysts agrees very well with that of the weighted average on the individual metal catalysts and this may be taken as a kinetic evidence for the absence of coclusters. Carbon monoxide methanation activity of the bimetallic catalysts is quite similar to that of the supported platinum catalyst. 6 refs., 6 figs., 2 tabs.

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.

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

Directory of Open Access Journals (Sweden)

Bamidele V. Ayodele

2016-08-01

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

NiCo as catalyst for magnetically induced dry reforming of methane

Science.gov (United States)

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

2018-03-01

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

Interfacial reactions between DBD and porous catalyst in dry methane reforming

Science.gov (United States)

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

2018-03-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-01-15

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

Effect of Ca, Ce or K oxide addition on the activity of Ni/SiO{sub 2} catalysts for the methane decomposition reaction

Energy Technology Data Exchange (ETDEWEB)

Zapata, Beatriz; Torres-Garcia, Enelio [Instituto Mexicano del Petroleo, Programa de Procesos y Reactores, Eje C. 152, Mexico, D.F., C.P. 07730 (Mexico); Valenzuela, Miguel A.; Palacios, Jorge [Instituto Politecnico Nacional-ESIQIE, Lab. Catalisis y Materiales, Zacatenco, Mexico, D.F., C.P. 07738 (Mexico)

2010-11-15

To increase the activity and stability of Ni/SiO{sub 2} catalysts, a series of Ni-Ca, Ni-K and Ni-Ce promoted catalysts were prepared by successive impregnations. The textural properties, reducibility and catalytic performance in the methane decomposition reaction were investigated. The catalyst containing 30 wt.% Ni and 30 wt.% cerium oxide greatly increased the conversion of methane (90% of equilibrium value) and improved the stability, whereas the Ni-K and Ni-Ca were less active and stable than the Ni/SiO{sub 2} catalyst. The results suggest that Ce addition prevents the sintering of nickel particles during reduction process maintaining a random distribution between the silica and cerium oxide improving the distribution and migration of deposited carbon. (author)

Recent advances in methane activation

Energy Technology Data Exchange (ETDEWEB)

Huuska, M; Kataja, K [VTT Chemical Technology, Espoo (Finland)

1997-12-31

Considerable work has been done in the research and development of methane conversion technologies. Although some promising conversion processes have been demonstrated, further advances in engineering and also in the chemistry are needed before these technologies become commercial. High-temperature processes, e.g. the oxidative coupling of methane, studied thoroughly during the last 15 years, suffer from severe theoretical yield limits and poor economics. In the long term, the most promising approaches seem to be the organometallic and, especially, the biomimetic activation of methane. (author) (22 refs.)

Recent advances in methane activation

Energy Technology Data Exchange (ETDEWEB)

Huuska, M.; Kataja, K. [VTT Chemical Technology, Espoo (Finland)

1996-12-31

Considerable work has been done in the research and development of methane conversion technologies. Although some promising conversion processes have been demonstrated, further advances in engineering and also in the chemistry are needed before these technologies become commercial. High-temperature processes, e.g. the oxidative coupling of methane, studied thoroughly during the last 15 years, suffer from severe theoretical yield limits and poor economics. In the long term, the most promising approaches seem to be the organometallic and, especially, the biomimetic activation of methane. (author) (22 refs.)

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)

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-04-15

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-07-01

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

Metalloporphyrins immobilized in Fe3O4@SiO2 mesoporous submicrospheres: Reusable biomimetic catalysts for hydrocarbon oxidation.

Science.gov (United States)

Barbosa, Isaltino A; de Sousa Filho, Paulo C; da Silva, Douglas L; Zanardi, Fabrício B; Zanatta, Lucas D; de Oliveira, Adilson J A; Serra, Osvaldo A; Iamamoto, Yassuko

2016-05-01

We successfully immobilized metalloporphyrins (MeP) in mesoporous silica coating magnetite spheres. In this sense, we prepared two different classes of core@shell supports, which comprise aligned (Fe3O4-AM-MeP, MeP=FeP or MnP) and non-aligned (Fe3O4-NM-MeP, MeP=FeP or MnP) mesoporous magnetic structures. X-ray diffractometry and energy dispersive X-ray spectroscopy confirmed the mesoporous nature of the silica shell of the materials. Magnetization measurements, scanning and transmission electron microscopies (SEM/TEM), electrophoretic mobility (ζ-potential), and infrared spectroscopy (FTIR) also confirm the composition and structure of the materials. The catalysts maintained their catalytic activity during nine reaction cycles toward hydrocarbon oxidation processes without detectable catalyst leaching. The catalysis results revealed a biomimetic pattern of cytochrome P450-type enzymes, thus confirming that the prepared materials are can effectively mimic the activity of such groups. Copyright © 2016 Elsevier Inc. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

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

1995-12-31

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

Cationic Zn-Porphyrin Polymer Coated onto CNTs as a Cooperative Catalyst for the Synthesis of Cyclic Carbonates.

Science.gov (United States)

Jayakumar, Sanjeevi; Li, He; Chen, Jian; Yang, Qihua

2018-01-24

The development of solid catalysts containing multiple active sites that work cooperatively is very attractive for biomimetic catalysis. Herein, we report the synthesis of bifunctional catalysts by supporting cationic porphyrin-based polymers on carbon nanotubes (CNTs) using the direct reaction of 5,10,15,20-tetrakis(4-pyridyl)porphyrin zinc(II), di(1H-imidazol-1-yl)methane, and 1,4-bis(bromomethyl)benzene in the presence of CNTs. The bifunctional catalysts could efficiently catalyze the cycloaddition reaction of epoxides and CO 2 under solvent-free conditions with porphyrin zinc(II) as the Lewis acid site and a bromine anion as a nucleophilic agent working in a cooperative way. Furthermore, a relative amount of porphyrin zinc(II) and quaternary ammonium bromide could be facilely adjusted for facilitating cooperative behavior. The bifunctional catalyst with a TOF up to 2602 h -1 is much more active than the corresponding homogeneous counterpart and is one of the most active heterogeneous catalysts ever reported under cocatalyst-free conditions. The high activity is mainly attributed to the enhanced cooperation effect of the bifunctional catalyst. With a wide substrate scope, the bifunctional catalyst could be stably recycled. This work demonstrates a new approach for the generation of a cooperative activation effect for solid catalysts.

Lithium chemistry of lithium doped magnesium oxide catalysts used in the oxidative coupling of methane

NARCIS (Netherlands)

Korf, S.J.; Roos, J.A.; de Bruijn, N.A.; van Ommen, J.G.; Ross, J.R.H.

1990-01-01

Active sites are created on the surface of a Li/MgO catalyst used for the selective oxidation of methane by the gradual loss of carbon dioxide from surface carbonate species in the presence of oxygen. Decomposition of the carbonate species in the absence of oxygen is detrimental to the activity of

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

Directory of Open Access Journals (Sweden)

Takeshi Fujita

2017-10-01

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

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

OpenAIRE

Yanyan Feng; Wen Yang; Wei Chu

2015-01-01

This work studied the influence of textural characteristics of CNTs on catalytic performance of Ni/CNTs for CO2 methanation. The CNTs supports were prepared by chemical vapor deposition method using Ni/MgO catalysts, and acetonitrile and ethanol were used as carbon sources, respectively. The Ni/CNTs catalysts were prepared via impregnation method and characterized by X-ray diffraction (XRD), N2 adsorption/desorption, and temperature-programmed reduction (H2-TPR) techniques. The results indica...

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.

Drip irrigation emitter clogging in Dutch greenhouses as affected by methane and organic acids

NARCIS (Netherlands)

Kreij, de C.; Burg, van der A.M.M.; Runia, W.T.

2003-01-01

It is believed that the serious clogging of drip irrigation emitters in the Dutch greenhouse industry is caused by methane-oxidising bacteria and/or organic acids used as anti-clogging agents. In this study greenhouses with moderate to severe emitter clogging have been examined. High methane

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.

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

NARCIS (Netherlands)

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

1993-01-01

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

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.

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.

Oxidative coupling of methane. Still a challenge for catalyst development and reaction engineering

Energy Technology Data Exchange (ETDEWEB)

Schomaecker, R.; Arnd, S.; Beck, B. [Technical Univ. of Berlin (Germany). Dept. of Chemistry] [and others

2013-11-01

The oxidative coupling of methane to ethylene offers great industrial potential, because it would broaden the feedstock basis for chemical industry. Because methane is the most stable hydrocarbon, its activation requires high temperatures and it is a great scientific challenge to overcome the apparent yield limit of about 25%. This barrier has never been exceeded since the beginning of OCM research more than 20 years ago. Results and Discussion: This challenge is one of the key projects of the Cluster of Excellence UNICAT and requires joined efforts and contributions from many disciplines, because this reaction shows a combined surface/gas phase reaction mechanism which results in very unusual and complex dependencies on the reaction conditions. Although dozens of materials are known to catalyze the reaction, the selection of a catalyst suitable for an industrial process is difficult, due to severe stability problems of many materials. Li/MgO was chosen by the UNICAT-team as model catalyst, because of the extended literature about it. But it shows uncontrollable deactivation, no matter what precursor and method were used for its preparation. Nevertheless, it is a suitable catalyst for fundamental studies, due to its formal chemical simplicity. A key result of the joined research activities was the disproval of the Lunsford mechanism and the elucidation of the real function of lithium as a surface modifier creating a rough and defect-rich surface. For the development of an OCM process another catalyst, Na{sub 2}WO{sub 4}/Mn/SiO{sub 2}, was chosen from the rich literature on OCM. Although less is known about its structure and the reaction mechanism at this catalyst, its stability was the most important reason to select it for further engineering studies. Kinetic isotope measurements and studies in a TAP reactor demonstrate the similarity of the reaction mechanisms at both catalysts, despite the completely different materials. The selectivity is largely controlled by

Ni{sub x}Al{sub y} hydrotalcites derived catalysts for methane dry reforming reaction

Energy Technology Data Exchange (ETDEWEB)

Touahra, F.; Abdessadek, Z.; Saadi, A.; Cherifi, O.; Halliche, D. [Univ. des Sciences et de la Technologie Houari Boumedienne (USTHB), El-Alia, Alger (Algeria); Bachari, K. [Centre de Recherche Scientifique et Technique en Analyse Physico-Chimique (CRAPC), Alger (Algeria)

2010-07-01

CO{sub 2} reforming of methane shows a growing interest from both industrial and environmental viewpoint. Form an environmental perspective, CO{sub 2} and CH{sub 4} are undesirable greenhouse gases and both are consumed by the proposed reaction. The purpose of this paper is to study the effect of varying molar ratio R=Ni{sup 2+}/Al{sup 3+}(R=2, 3, 5, 7 and 9) for CO{sub 2} reforming of methane reaction. The corresponding Ni{sub x}Al{sub y} samples were prepared by coprecipitation at constant basic pH and calcined at 800 C. They were characterized by ICP method, X-Ray powder diffraction patterns, BET method and FTIR. We have studied the reaction of dry reforming of methane by carbon dioxide in presence of the various catalysts at temperatures ranging from 400 to 700 C. A high conversions to natural conversions were obtained when R>5. (orig.)

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-04-15

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

Novel metalloporphyrin catalysts for the oxidation of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Showalter, M.C.; Nenoff, T.M.; Shelnutt, J.A.

1996-11-01

Work was done for developing biomimetic oxidation catalysts. Two classes of metalloporphyrin catalysts were studied. The first class of catalysts studied were a novel series of highly substituted metalloporphyrins, the fluorinated iron dodecaphenylporphyrins. These homogeneous metalloporphyrin catalysts were screened for activity as catalysts in the oxidation of hydrocarbons by dioxygen. Results are discussed with respect to catalyst structural features. The second type of catalysts studied were heterogeneous catalysts consisting of metalloporphyrins applied to inorganic supports. Preliminary catalytic testing results with these materials are presented.

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Energy Technology Data Exchange (ETDEWEB)

Huang, Guan, E-mail: huangg66@126.com; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-30

Graphical abstract: A biomimetic catalyst of iron-tetrakis(4-sulfonatophenyl)porphyrin immobilized on powdered chitosan achieves efficient cyclohexane oxidation with high ketone and alcohol yields. - Highlights: • Fe (TPPS)/pd-CTS is an excellent catalyst for cyclohexane oxidation. • Amino ligation alters the electron cloud density around the iron cation. • Amino coordination likely reduces the activation energy of Fe (TPPS). • The catalyst achieved 22.9 mol% yields of cyclohexanone and cyclohexanol. - Abstract: This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O{sub 2}. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

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

KAUST Repository

Liang, Yin; Li, Zhikao; Nourdine, Mohamed; Shahid, Salman; Takanabe, Kazuhiro

2014-01-01

A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-07-01

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

Catalytic efficiency of natural and synthetic compounds used as laccase-mediators in oxidising veratryl alcohol and a kraft lignin, estimated by electrochemical analysis

International Nuclear Information System (INIS)

Gonzalez Arzola, K.; Arevalo, M.C.; Falcon, M.A.

2009-01-01

The electrochemical properties of eighteen natural and synthetic compounds commonly used to expand the oxidative capacity of laccases were evaluated in an aqueous buffered medium using cyclic voltammetry. This clarifies which compounds fulfil the requisites to be considered as redox mediators or enhancers. Cyclic voltammetry was also applied as a rapid way to assess the catalytic efficiency (CE) of those compounds which oxidise a non-phenolic lignin model (veratryl alcohol, VA) and a kraft lignin (KL). With the exception of gallic acid and catechol, all assayed compounds were capable of oxidising VA with varying CE. However, only some of them were able to oxidise KL. Although the oxidised forms of HBT and acetovanillone were not electrochemically stable, their reduced forms were quickly regenerated in the presence of VA. They thus act as chemical catalysts. Importantly, HBT and HPI did not attack the KL via the same mechanism as in VA oxidation. Electrochemical evidence suggests that violuric acid oxidises both substrates by an electron transfer mechanism, unlike the other N-OH compounds HBT and HPI. Acetovanillone was found to be efficient in oxidising VA and KL, even better than the synthetic mediators TEMPO, violuric acid or ABTS. Most of the compounds produced a generalised increase in the oxidative charge of KL, probably attributed to chain reactions arising between the phenolic and non-phenolic components of this complex molecule

Catalytic efficiency of natural and synthetic compounds used as laccase-mediators in oxidising veratryl alcohol and a kraft lignin, estimated by electrochemical analysis

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Arzola, K. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain); Arevalo, M.C. [Department of Physical Chemistry, Faculty of Chemistry, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: carevalo@ull.es; Falcon, M.A. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: mafalcon@ull.es

2009-03-30

The electrochemical properties of eighteen natural and synthetic compounds commonly used to expand the oxidative capacity of laccases were evaluated in an aqueous buffered medium using cyclic voltammetry. This clarifies which compounds fulfil the requisites to be considered as redox mediators or enhancers. Cyclic voltammetry was also applied as a rapid way to assess the catalytic efficiency (CE) of those compounds which oxidise a non-phenolic lignin model (veratryl alcohol, VA) and a kraft lignin (KL). With the exception of gallic acid and catechol, all assayed compounds were capable of oxidising VA with varying CE. However, only some of them were able to oxidise KL. Although the oxidised forms of HBT and acetovanillone were not electrochemically stable, their reduced forms were quickly regenerated in the presence of VA. They thus act as chemical catalysts. Importantly, HBT and HPI did not attack the KL via the same mechanism as in VA oxidation. Electrochemical evidence suggests that violuric acid oxidises both substrates by an electron transfer mechanism, unlike the other N-OH compounds HBT and HPI. Acetovanillone was found to be efficient in oxidising VA and KL, even better than the synthetic mediators TEMPO, violuric acid or ABTS. Most of the compounds produced a generalised increase in the oxidative charge of KL, probably attributed to chain reactions arising between the phenolic and non-phenolic components of this complex molecule.

Near room temperature chemical vapor deposition of graphene with diluted methane and molten gallium catalyst.

Science.gov (United States)

Fujita, Jun-Ichi; Hiyama, Takaki; Hirukawa, Ayaka; Kondo, Takahiro; Nakamura, Junji; Ito, Shin-Ichi; Araki, Ryosuke; Ito, Yoshikazu; Takeguchi, Masaki; Pai, Woei Wu

2017-09-28

Direct growth of graphene integrated into electronic devices is highly desirable but difficult due to the nominal ~1000 °C chemical vapor deposition (CVD) temperature, which can seriously deteriorate the substrates. Here we report a great reduction of graphene CVD temperature, down to 50 °C on sapphire and 100 °C on polycarbonate, by using dilute methane as the source and molten gallium (Ga) as catalysts. The very low temperature graphene synthesis is made possible by carbon attachment to the island edges of pre-existing graphene nuclei islands, and causes no damages to the substrates. A key benefit of using molten Ga catalyst is the enhanced methane absorption in Ga at lower temperatures; this leads to a surprisingly low apparent reaction barrier of ~0.16 eV below 300 °C. The faster growth kinetics due to a low reaction barrier and a demonstrated low-temperature graphene nuclei transfer protocol can facilitate practical direct graphene synthesis on many kinds of substrates down to 50-100 °C. Our results represent a significant progress in reducing graphene synthesis temperature and understanding its mechanism.

Catalytic Combustion of Low Concentration Methane over Catalysts Prepared from Co/Mg-Mn Layered Double Hydroxides

Directory of Open Access Journals (Sweden)

Hongfeng Liu

2014-01-01

Full Text Available A series of Co/Mg-Mn mixed oxides were synthesized through thermal decomposition of layered double hydroxides (LDHs precursors. The resulted catalysts were then subjected for catalytic combustion of methane. Experimental results revealed that the Co4.5Mg1.5Mn2LDO catalyst possessed the best performance with the T90=485°C. After being analyzed via XRD, BET-BJH, SEM, H2-TPR, and XPS techniques, it was observed that the addition of cobalt had significantly improved the redox ability of the catalysts whilst certain amount of magnesium was essential to guarantee the catalytic activity. The presence of Mg was helpful to enhance the oxygen mobility and, meanwhile, improved the dispersion of Co and Mn oxides, preventing the surface area loss after calcination.

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.

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)

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.

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...

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.

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.

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

KAUST Repository

Zhou, Lu; Enakonda, Linga Reddy; Li, Sheng; Gary, Daniel; Del-Gallo, Pascal; Mennemann, Christina; Basset, Jean-Marie

2018-01-01

In this work, for the first time, iron ores with 91.7%–96.2% FeO, 1.3%–2.3% AlO, 1.2%–4.5% SiO, 1.3%–3.9% NaO, were studied directly as bulk catalysts for methane decomposition. By hydrogen pre-reduction at 850 °C, FeO species on iron ores were

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.

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

Small Molecule Catalysts for Harvesting Methane Gas

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-06

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

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

Directory of Open Access Journals (Sweden)

Yanyan Feng

2015-01-01

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

Deactivation of nickel catalysts in the methanization of hydrogen/carbon monoxide mixtures under pressure

Energy Technology Data Exchange (ETDEWEB)

Zeeb, H P

1979-01-01

The deactivation course of nickel methanization catalysts was investigated in the temperature range of 310/sup 0/C to 370/sup 0/C and in the pressure region of 20 to 80 bar. Raising the CO partial pressure accelerated the deactivation whereas raising the H/sub 2/ partial pressure slowed it down. An influence of the temperature could not be clearly recognized. The deactivation got slower with greater dwell time and larger degree of conversion. Two hypotheses to explain the deactivation are given.

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.

Effect of additives on lithium doped magnesium oxide catalysts used in the oxidative coupling of methane

NARCIS (Netherlands)

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

1989-01-01

It has been found that it is possible to improve the activity and stability for the oxidative coupling of methane of a Li/MgO catalyst by the addition of small amounts of the oxides of various transition and rare earth metals. A number of these additives, e.g. SnO2, TiO2, Dy2O3 and Tb4O7, caused

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.

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

Directory of Open Access Journals (Sweden)

Vesna Nikolić

2015-03-01

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

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

Science.gov (United States)

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

2018-05-01

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

Biomimetic synthesis of cellular SiC based ceramics from plant ...

Indian Academy of Sciences (India)

Unknown

SiC based materials so derived can be used in structural applications and in designing high temperature filters and catalyst supports. Keywords. Biomimetic synthesis; carbonaceous biopreform; biomorphic Si–SiC ceramic composites; porous cellular SiC ceramics. 1. Introduction. In recent years, there has been tremendous ...

Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts

DEFF Research Database (Denmark)

Marsden, Charlotte Clare; Taarning, Esben; Hansen, David

2008-01-01

A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient cond...... conditions; the reactions can be performed in an open flask and at room temperature. Benzaldehyde is even oxidised at a reasonable rate below -70 degrees C. Acrolein is oxidised to methyl acrylate in high yield using the same protocol.......A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient...

Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

KAUST Repository

Khan, Abdulaziz M.

2016-04-26

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

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

Science.gov (United States)

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

2015-12-29

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

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

Science.gov (United States)

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

2018-03-01

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

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.

Catalyst study for the plasma exhaust purification process

International Nuclear Information System (INIS)

Chabot, J.; Sannier, J.

1990-01-01

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

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)

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)

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-05-15

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

The support effect of the Mn-Na{sub 2}WO{sub 4}/SiO{sub 2} catalyst in the oxidative coupling of methane

Energy Technology Data Exchange (ETDEWEB)

Yildiz, M.; Arndt, S.; Simon, U.; Aksu, Y.; Schubert, H.; Schomaecker, R. [Technische Univ. Berlin (Germany)

2011-07-01

Methane is the major component of natural gas with known resources rivaling those of crude oil. Therefore, a direct conversion of CH{sub 4} into value added products is of strong interest for the chemical industry. One suitable reaction is the oxidative coupling of methane, which has received great attention since the first publications. Despite the intensive research, this process is not applied yet due to a lack of active and stable catalysts. A promising candidate is the Mn-Na{sub 2}WO{sub 4}/SiO{sub 2} catalyst, which is known for its high selectivity and its remarkable stability. Although there are some suggestions on the role of the different components, the support material and the phase of the support material, reliable facts are rare for this catalyst. For this reason we carried out a wide-range variation of the support material (e.g. ZrO{sub 2}, Fe{sub 2}O{sub 3}, TiO{sub 2}, Al{sub 2}O{sub 3}, MgO, etc.) to reveal its effect to the activity and the stability. The prepared catalysts were characterized by BET surface area and X-ray diffraction analysis and the OCM was performed in a packed-bed reactor with respect to long term stability. We found that the catalyst is active in the OCM even without SiO{sub 2} as support material, questioning the current suggestions for the active center. (orig.)

Surface spectroscopic characterization of a model methane-activation catalyst

International Nuclear Information System (INIS)

Chen, J.G.; Weisel, M.D.; Hoffmann, F.M.; Hall, R.B.

1992-01-01

In an effort to understand the details concerning the alkali-promoted selectivity for the oxidative coupling of methane, the authors have carried out a detailed characterization of a model K/NiO/Ni(100) catalyst under well-controlled, ultrahigh vacuum conditions. The authors' systematic approach involved the following procedures: detailed investigation of the formation and structure of NiO on a clean Ni(100) surface; spectroscopic characterization of K-doped NiO by in situ deposition of potassium onto well-characterized NiO/Ni(100) substrate; and determination of the reactivities of NiO/Ni(100) and K/NiO/Ni(100) towards H 2 and CH 4 . In this paper, the authors will use the model K/NiO/Ni(100) system as an example to demonstrate that a detailed, complementary characterization of the model catalyst could best be achieved by using a combination of a variety of surface techniques: The methods of HREELS, LEED, XPS and AES could be applied to obtain properties on and near the surface regions; the technique of FYNES, being a photon-in/photon-out method could be utilized to investigate the bulk properties up to 2000 Angstrom below the surface; the method of FTIR using CO as a probing molecule is, on the other hand, sensitive only to the properties of the top-most surface layer. The result is to be presented in this paper will be mainly those obtained by using the two vibrational spectroscopies (HREELS and FTIR). Results from other surface techniques will also be discussed or presented when they provide additional information to the vibrational data

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

Science.gov (United States)

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

2018-03-01

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

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.

Study of polyoxide catalysts of methane combustion on Mn, Cu, Ni, rare earth elements, alkaline earth elements base by the X-ray fluorescence analysis method

International Nuclear Information System (INIS)

Grigor'eva, V.P.; Popova, N.M.; Zheksenbaeva, Z.T.; Sass, A.S.; Salakhova, R.Kh.; Dosumov, K.D.

2002-01-01

The results of X-ray fluorescence analysis of polyoxide catalysts on of Mn, Cu, Ni, rare earth elements, alkaline earth elements base supported on 2 % Ce/θ-Al 2 O 3 are presented. This polyoxide catalysts are using for deep methane oxidation. DRON-4-7 X-ray diffractometers was applied for the analysis. It was found, that oxides in Ni-Cu-Cr catalysts after long time heating up to 1200 deg. C have been interacted with catalyst supports with Ni(Cu)Al 2 O 3 aluminates formation and due to its decomposition transformation degree of CH 4 to CO 2 are reduced. Activity of MnBaSrCeLa catalysts after heating up to 1200 deg. C does not changed

Deuterohemin-Peptide Enzyme Mimic-Embedded Metal-Organic Frameworks through Biomimetic Mineralization with Efficient ATRP Catalytic Activity.

Science.gov (United States)

Jiang, Wei; Wang, Xinghuo; Chen, Jiawen; Liu, Ying; Han, Haobo; Ding, Yi; Li, Quanshun; Tang, Jun

2017-08-16

An enzyme mimic harboring iron porphyrin (DhHP-6) embedded in zeolite imidazolate framework-8 (ZIF-8) was constructed through a biomimetic mineralization approach to obtain composite DhHP-6@ZIF-8. The composite was then used as a catalyst in the atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether methacrylate (PEGMA 500 ) in which poly(PEGMA 500 ) could be synthesized with monomer conversion of 76.1% and M n of 45 900 g/mol, stronger than that obtained when using free DhHP-6 as a catalyst. More importantly, it could efficiently overcome the drawbacks of free DhHP-6 and achieve the easy separation of DhHP-6 from the catalytic system and the elimination of iron residues in the synthesized polymer. In addition, it exhibited an enhanced recyclability with monomer conversion of 75.7% after five cycles and favorable stability during the ATRP reaction with mimic-ZIF-8 composite developed through biomimetic mineralization can be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications.

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)

Synthesis of cationic dibenzosemibullvalene-based phase-transfer catalysts by di-π-methane rearrangements of pyrrolinium-annelated dibenzobarrelene derivatives

Directory of Open Access Journals (Sweden)

Jia Luo

2011-01-01

Full Text Available Dibenzobarrelene derivatives, that are annelated with a pyrrolinium unit [N,N-dialkyl-3,4-(9',10'-dihydro-9',10'-anthraceno-3-pyrrolinium derivatives], undergo a photo-induced di-π-methane rearrangement upon triplet sensitization to give the corresponding cationic dibenzosemibullvalene derivatives [N,N-dialkyl-3,4-{8c,8e-(4b,8b-dihydrodibenzo[a,f]cyclopropa[cd]pentaleno}pyrrolidinium derivatives]. Whereas the covalent attachment of a benzophenone functionality to the pyrrolinium nitrogen atom did not result in an internal triplet sensitization, the introduction of a benzophenone unit as part of the counter ion enables the di-π-methane rearrangement of the dibenzobarrelene derivative in the solid-state. Preliminary experiments indicate that a cationic pyrrolidinium-annelated dibenzosemibullvalene may act as phase-transfer catalyst in alkylation reactions.

Oscillatory Behavior during the Catalytic Partial Oxidation of Methane: Following Dynamic Structural Changes of Palladium Using the QEXAFS Technique

DEFF Research Database (Denmark)

Stoetzel, Jan; Frahm, Ronald; Kimmerle, Bertram

2012-01-01

oxidation of methane, the catalyst reduced from the end to the beginning of the catalyst bed and oxidized again toward the end as soon as the entire catalyst bed was reduced. On an entirely oxidized catalyst bed, only total oxidation of methane was observed and consumed the oxygen until the conditions...... of the Pd particles at increasing age of the catalyst was observed, which leads to a lower oscillation frequency. Effects of particle size, oven temperature, and oxygen/methane ratio on the oscillation behavior were studied in detail. The deactivation period (reoxidation of Pd) was much less influenced...... by the oven temperature than the ignition behavior of the catalytic partial oxidation of methane. This indicates that deactivation is caused by an autoreduction of the palladium at the beginning of the catalyst bed due to the high temperature achieved by total oxidation of methane....

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-07-22

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

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)

Selective Oxidations using Nanostructured Heterogeneous Catalysts

DEFF Research Database (Denmark)

Mielby, Jerrik Jørgen

and because they produce H2O as the only by-product. Chapter 1 gives a short introduction to basic concepts in heterogeneous catalysis and green chemistry. Furthermore, the chapter gives an overview of the most important strategies to synthesise functional nanostructured materials and highlights how detailed......The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available...... understanding of size, shape and structure can help in the development of new and more efficient heterogeneous catalysts. The chapter is not intended to give a complete survey, but rather to introduce some of the recent developments in the synthesis of nanostructured heterogeneous catalysts. Finally...

Methane anomalies in seawaters of the Ragay Gulf, Philippines: methane cycling and contributions to atmospheric greenhouse gases

International Nuclear Information System (INIS)

Heggie, D.T.; Evans, D.; Bishop, J.H.

1999-01-01

The vertical distribution of methane has been measured in the water column of a semi-enclosed basin, the Ragay Gulf, in the Philippines archipelago. The methane distribution is characterised by unusual mid-water and bottom-water plumes, between 80 and 100 m thick. The plumes are confined to water depths between about 100 and 220 m. where the temperature-depth (a proxy for seawater density) gradient is steepest. Plumes of high methane are 'trapped' within the main thermocline; these are local features, persisting over kilometre-scale distances. Geochemical and geological evidence suggests that the elevated methane concentrations are thermogenic in origin (although an oxidised biogenic origin cannot be ruled out for some of the methane anomalies), and have migrated from the sea floor into the overlying water. The mid and bottom-water methane maxima support fluxes of methane from depth into surface waters and, subsequently, from the oceans to the atmosphere. The average supersaturation of methane in the top 5 m of the sea, at nine locations, was 206±16.5%; range 178-237%. The average estimated sea-air flux was 101 nmole.cm -2 .y -1 and probably represents a minimum flux, because of low wind speeds of <10 knots. These fluxes, we suggest, are supported by seepage from the sea floor and represent naturally occurring fluxes of mostly fossil methane (in contrast to anthropogenic fossil methane), from the sea to the atmosphere. The estimated minimum fluxes of naturally occurring fossil methane are comparable to those biogenic fluxes measured elsewhere in the surface oceans, but are less than those naturally occurring methane inputs from sediments of the Barents Sea. Ragay Gulf fluxes are also less than anthropogenic fluxes measured in areas of petroleum exploration and development, such as the Texas and Louisiana, USA shelf areas

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

Directory of Open Access Journals (Sweden)

Xiaoke Fang

2016-01-01

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

Development of oxidised and heat-moisture treated potato starch film.

Science.gov (United States)

Zavareze, Elessandra da Rosa; Pinto, Vânia Zanella; Klein, Bruna; El Halal, Shanise Lisie Mello; Elias, Moacir Cardoso; Prentice-Hernández, Carlos; Dias, Alvaro Renato Guerra

2012-05-01

This study investigated the effects of sodium hypochlorite oxidation and a heat-moisture treatment of potato starch on the physicochemical, pasting and textural properties of potato starches in addition to the water vapour permeability (WVP) and mechanical properties of potato starch films produced from these starches. The carbonyl contents, carboxyl contents, swelling power, solubility, pasting properties and gel texture of the native, oxidised and heat-moisture treated (HMT) starches were evaluated. The films made of native, oxidised and HMT starches were characterised by thickness, water solubility, colour, opacity, mechanical properties and WVP. The oxidised and HMT starches had lower viscosity and swelling power compared to the native starch. The films produced from oxidised potato starch had decreased solubility, elongation and WVP values in addition to increased tensile strength compared to the native starch films. The HMT starch increased the tensile strength and WVP of the starch films compared to the native starch. Copyright © 2011 Elsevier Ltd. All rights reserved.

Advanced Heterogeneous Fenton Treatment of Coalbed Methane-Produced Water Containing Fracturing Fluid

Directory of Open Access Journals (Sweden)

Meng Zhang

2018-04-01

Full Text Available This study investigated the heterogeneous Fenton treatment to process coalbed methane-produced water containing fracturing fluid and chose the development region of coalbed methane in the Southern Qinshui Basin as a research area. We synthesized the catalyst of Fe-Co/γ-Al2O3 by homogeneous precipitation method and characterized it by BET, XRD, SEM-EDS, FTIR, and XPS. Based on the degradation rate, we studied the influences of the heterogeneous Fenton method on the coalbed methane output water treatment process parameters, including initial pH, H2O2 concentration, and the catalyst concentration. We also investigated the impacts of overall reaction kinetics of heterogeneous catalytic oxidation on coalbed methane-produced water containing fracturing fluid. Results showed that Fe-Co/γ-Al2O3 as a Fenton catalyst has a good catalytic oxidation effect and can effectively process coalbed methane-produced water. This reaction also followed first-order kinetics. The optimal conditions were as follows: the initial pH of 3.5, a H2O2 concentration of 40 mol L−1, a catalyst concentration of 4 g/L, and an apparent reaction rate constant of 0.0172 min−1. Our results provided a basis to establish methods for treating coalbed methane-produced water.

A comparative study of the mechanical behaviour of thermally oxidised commercially pure titanium and zirconium.

Science.gov (United States)

Alansari, A; Sun, Y

2017-10-01

The objective of this study is to compare the mechanical behaviour of thermally oxidised commercially pure titanium (CP-Ti) and commercially pure zirconium (CP-Zr). For this purpose, these two bio-metals were thermally oxidised under the same condition (650°C for 6h) and the oxidised specimens were characterised using various analytical and experimental techniques, including oxygen uptake analysis, layer thickness and hardness measurements, scratch tests, dry sliding friction and wear tests and tribocorrosion tests in Ringer's solution. The results show that under the present thermal oxidation condition, 4 times more oxygen is introduced into CP-Zr than into CP-Ti and the oxide layer produced on CP-Zr is nearly 6 times thicker than that on CP-Ti. Thermally oxidised CP-Zr possesses a higher hardness, a deeper hardening depth and better scratch resistance than thermally oxidised CP-Ti. Under dry sliding and tribocorrosion conditions, thermally oxidised CP-Zr also possesses much better resistance to material removal and a higher load bearing capacity than thermally oxidised CP-Ti. Thus, thermally oxidised Zr possesses much better mechanical behaviour than thermally oxidised Ti. Copyright © 2017 Elsevier Ltd. All rights reserved.

Plasma catalytic process for CO2 methanation

International Nuclear Information System (INIS)

Nizio, Magdalena

2016-01-01

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

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

Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

Science.gov (United States)

Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

2015-03-20

A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

The interfacial capacitance of an oxidised polycrystalline gold electrode in an aqueous HClO4 electrolyte

International Nuclear Information System (INIS)

Grdeń, M.

2013-01-01

The interfacial capacitance of a polycrystalline gold electrode electrochemically oxidised in an aqueous 0.1 M HClO 4 electrolyte has been investigated by means of the electrochemical impedance spectroscopy. From 1.3 to 3 monolayers of Au atoms were oxidised under constant potential conditions and for various oxidation times. The capacitance of the oxidised layers was analysed as a function of the electrode potential and the extent of the surface oxidation. It was found that the interfacial capacitance decreases upon surface oxidation. The components of the interfacial capacitance of the oxidised layer: the double layer capacitance and the capacitance of the oxidised layer; have been separated. The capacitance of the double layer of the oxidised surface was found to be comparable to the capacitance measured for the metallic surface. - Highlights: • The impedance spectra for thin layers of Au oxides/hydroxides were acquired. • Separate determination of the double layer and the oxide capacitances of oxidised Au • The double layer capacitances of oxidised and non-oxidised Au surfaces are comparable

Selective CO Methanation on Highly Active Ru/TiO2 Catalysts: Identifying the Physical Origin of the Observed Activation/Deactivation and Loss in Selectivity

DEFF Research Database (Denmark)

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

2018-01-01

Ru /TiO2 catalysts are highly active and selective in the selective methanation of CO in the presence of large amounts of CO2, but suffer from a considerable deactivation and loss of selectivity during time on stream. Aiming at a fundamental understanding of these processes, we have systematically...... different effects such as structural effects, adlayer effects such as site blocking effects and changes in the chemical (surface) composition of the catalysts. Operando XANES / EXAFS measurements revealed that an initial activation phase is largely due to the reduction of oxidized Ru species, together...

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.

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

Science.gov (United States)

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

2017-11-22

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

Bifunctional cobalt F-T catalysts

Energy Technology Data Exchange (ETDEWEB)

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

1986-03-01

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

Li-doped MgO as catalysts for oxidative coupling of methane: A positron annihilation study

Science.gov (United States)

Dai, G. H.; Yan, Q. J.; Wang, Y.; Liu, Q. S.

1991-08-01

Magnesium oxides intentionally doped with lithium (with a maximum Li content of 40 tool%) for use as catalysts for oxidative coupling of methane were characterized by means of positron annihilation. The positron lifetime spectra, which could be reasonably well interpreted within the framework of the well-known trapping model, depend on the amount of Li doping of the MgO suggesting that positrons are trapped at dispersed small Li 2CO 3 precipitates. Very similar dependencies on lithium doping of the C 2 selectivity and the positron trapping rate ϰ imply an intimate relationship between the concentration of [Li] 0-centers (also referred to as [Li +O -] centers) and the selective activity of Li/MgO during catalytic reactions.

Methanation of Carbon Dioxide

OpenAIRE

Goodman, Daniel Jacob

2013-01-01

The emission of greenhouse gases into the atmosphere has been linked to global warming. Carbon dioxide's (CO2) one of the most abundant greenhouse gases. Natural gas, mainly methane, is the cleanest fossil fuel for electricity production helping meet the United States ever growing energy needs. The methanation of CO2 has the potential to address both of these problems if a catalyst can be developed that meets the activity, economic and environmental requirements to industrialize the process. ...

Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst

DEFF Research Database (Denmark)

Nielsen, Inger Staunstrup; Taarning, Esben; Egeblad, Kresten

2007-01-01

Methyl esters can be produced in high yield by oxidising methanolic solutions of primary alcohols with dioxygen over a heterogeneous gold catalyst. The versatility of this new methodology is demonstrated by the fact that alkylic, benzylic and allylic alcohols, as well as alcohols containing...

Effects of oxidised oil and vitamin E on performance and some blood ...

African Journals Online (AJOL)

oxidised dietary oil and vitamin E supplementation could be determined on the performance, lipid peroxidation, antioxidant defence system and some blood and meat quality traits of broilers. Broilers were fed grower diets containing fresh or oxidised ...

Catalytic reduction of NO by methane using a Pt/C/polybenzimidazole/Pt/C fuel cell

DEFF Research Database (Denmark)

Petrushina, Irina; Cleemann, Lars Nilausen; Refshauge, Rasmus

2007-01-01

with participation of H+ or electrochemically produced hydrogen. When added, methane partially suppresses the electrochemical reduction of NO. Methane outlet concentration monitoring has shown the CH4 participation in the chemical catalytic reduction, i.e., methane co-adsorption with NO inhibited the electrochemical...... NO reduction and introduced a dominant chemical path of the NO reduction. The products of the NO reduction with methane were N2, C2H4, and water. The catalytic NO reduction by methane was promoted when the catalyst was negatively polarized (−0.2 V). Repeated negative polarization of the catalyst increased...

Lithium/magnesium oxide catalyst and method of making

Energy Technology Data Exchange (ETDEWEB)

Lunsford, J.H.; Hinson, P.G.

1991-07-16

This patent describes a method for preparing a catalyst which is effective for converting methane to ethane and ethylene. It comprises mixing a solution of a magnesium alkoxide in an alcohol with a solution containing a source of lithium in an alcohol, to obtain a ratio of magnesium metal to lithium metal; hydrolyzing the magnesium alkoxide in the solution to form a gel; and calcining the gel to form a catalyst which is effective for converting methane to ethane and ethylene.

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

Energy Technology Data Exchange (ETDEWEB)

Kraemer, Michael

2008-04-15

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

Dry reforming of methane with CO{sub 2} at elevated pressures

Energy Technology Data Exchange (ETDEWEB)

Milanov, A.; Schwab, E.; Wasserschaff, G. [BASF SE, Ludwigshafen (Germany); Schunk, S. [hte AG, Heidelberg (Germany)

2013-11-01

The indirect conversion of natural gas into higher value chemicals and fuels via syngas is superior with regard to efficiency compared to the currently available direct conversion technologies and remains the industrially preferred route. Typically the syngas production route is generally dictated by the H{sub 2}/CO ratio requirements of the downstream synthesis process. Processes such as direct DME synthesis, high-temperature Fischer-Tropsch and acetic acid synthesis require CO rich syngas that is not readily accessible by established technologies like steam methane reforming (SMR) and autothermal reforming of methane (ATR). The CO{sub 2} reforming of methane, also known as dry reforming (DRM), is an attractive alternative technology for the production of CO-rich syngas. This paper gives an overview of the current joint research activities at BASF and hte AG aiming to develop suitable catalysts for CO{sub 2} reforming of methane at elevated pressures with minimized input of process steam. The performance profiles of two newly developed base metal catalysts are presented and discussed. The catalysts exhibit high degrees of methane and CO{sub 2} conversion in combination with an extraordinary coking resistance under high severity process conditions. (orig.)

Study and application of hydrophobic catalyst in treating tritium waste

International Nuclear Information System (INIS)

Dan, Gui-ping; Zhang, Dong; Qiu, Yong-mei; Yuan, Guo-Qi

2008-01-01

Tritium decontamination from tritium waste is important for the management of tritium waste. Tritium removal from waste tritium oxide can not only get tritium, but also reduce the amount of waste tritium. At the meantime, by cleaning the tritium pollution gas can also reduce the tritium exhausting from tritium facility. At present, the process of hydrogen isotopic exchange in tritium removal from waste tritium oxide and coordination oxidisation-adsorption in tritium cleaning from waste tritium gas are the mainly methods. In these methods, hydrophobic catalysts which can be used in these process are the key technology. There are many references about their preparing and applying, but few on the estimation about their performance changing during their applying. However, their performance stability on isotopic catalytic exchange and catalytic oxidisation will affect their using in reaction. Hydrophobic catalyst Pt-SDB which can be used in tritium isotopic exchange between tritium oxide and hydrogen and the cleaning of tritium pollution gas have been prepared in our laboratory in early days. In order to estimating their performance stability during their using, this work will investigate their stability on their catalytic activity and their radiation-resistance tritium. (author)

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.

Catalysis mechanism of Pd-promoted γ-alumina in the thermal decomposition of methane to hydrogen: A density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Salam, M. Abdus; Abdullah, Bawadi, E-mail: bawadi_abdullah@utp.edu.my

2017-02-15

Thermo-catalytic methane decomposition to elemental hydrogen mechanism in transitional metals (Pd, Ni & Mo) promoted Al{sub 2}O{sub 3} (001) catalyst have been studied using the density functional theory (DFT). Decomposition reactions are spontaneous and favourable above 775 K for all promoter. Pd-promoted Al{sub 2}O{sub 3} (001) catalyst demonstrates a breakthrough decomposition activity in hydrogen production as compared to Ni− and Mo-promoted Al{sub 2}O{sub 3} (001) catalysts. The activation energy (E{sub a}) range of the catalysis for Pd promoted Al{sub 2}O{sub 3} (001) catalysts is 0.003–0.34 eV. Whereas, Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts display activation energy E{sub a} in the range of 0.63–1.15 eV and 0.04–5.98 eV, respectively. Pd-promoted catalyst also shows a higher adsorption energy (−0.68 eV) and reactivity than that of Ni and Mo promoted Al{sub 2}O{sub 3} (001) catalysts. The rates of successive decomposition of methane are found to be 16.15 × 10{sup 12}, 15.95 × 10{sup 12} and 16.09 × 10{sup 12} s{sup −1} for the promoter of Pd, Ni and Mo, respectively. Pd promoted Al{sub 2}O{sub 3} (001) catalyst reduces the methane decomposition temperature (775 K) and deactivation rate significantly. The catalytic conditions and catalyst is promising in producing hydrogen to support hydrogen economy. - Highlights: • Transition metals (Pd, Ni & Mo) promoted γ-alumina catalysts are designed successfully. • Pd-promoted catalyst showed breakthrough activity in methane decomposition to hydrogen. • DFT study explored the catalysis mechanism of methane decomposition at atomic level. • Pd-promoted catalyst reduced temperature and activation barrier of methane decomposition reaction significantly.

Catalysis mechanism of Pd-promoted γ-alumina in the thermal decomposition of methane to hydrogen: A density functional theory study

International Nuclear Information System (INIS)

Salam, M. Abdus; Abdullah, Bawadi

2017-01-01

Thermo-catalytic methane decomposition to elemental hydrogen mechanism in transitional metals (Pd, Ni & Mo) promoted Al_2O_3 (001) catalyst have been studied using the density functional theory (DFT). Decomposition reactions are spontaneous and favourable above 775 K for all promoter. Pd-promoted Al_2O_3 (001) catalyst demonstrates a breakthrough decomposition activity in hydrogen production as compared to Ni− and Mo-promoted Al_2O_3 (001) catalysts. The activation energy (E_a) range of the catalysis for Pd promoted Al_2O_3 (001) catalysts is 0.003–0.34 eV. Whereas, Ni and Mo promoted Al_2O_3 (001) catalysts display activation energy E_a in the range of 0.63–1.15 eV and 0.04–5.98 eV, respectively. Pd-promoted catalyst also shows a higher adsorption energy (−0.68 eV) and reactivity than that of Ni and Mo promoted Al_2O_3 (001) catalysts. The rates of successive decomposition of methane are found to be 16.15 × 10"1"2, 15.95 × 10"1"2 and 16.09 × 10"1"2 s"−"1 for the promoter of Pd, Ni and Mo, respectively. Pd promoted Al_2O_3 (001) catalyst reduces the methane decomposition temperature (775 K) and deactivation rate significantly. The catalytic conditions and catalyst is promising in producing hydrogen to support hydrogen economy. - Highlights: • Transition metals (Pd, Ni & Mo) promoted γ-alumina catalysts are designed successfully. • Pd-promoted catalyst showed breakthrough activity in methane decomposition to hydrogen. • DFT study explored the catalysis mechanism of methane decomposition at atomic level. • Pd-promoted catalyst reduced temperature and activation barrier of methane decomposition reaction significantly.

Oxidative coupling of methane using inorganic membrane reactor

Energy Technology Data Exchange (ETDEWEB)

Ma, Y.H.; Moser, W.R.; Dixon, A.G. [Worcester Polytechnic Institute, MA (United States)] [and others

1995-12-31

The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.

Development of catalysts for chemical reactions driven by concentrated solar energy

International Nuclear Information System (INIS)

Berman, A.; Levitan, R.; Levy, M.

1992-03-01

The aim of this phase of the work is to study commercially available low priced catalysts, for the methanation and reforming processes in the closed-loop solar chemical heat pipe. This report summarized some long term tests of commercially available methanation catalysts and the measurement of their active surface before and after reaction. It was found that the 1%Ru on alumina stars catalysts (prepared by Englehard Company according to our request) is very active and stable at 350-750 C. The catalyst 'A' produced in Russia, is less active, however, did not lose the mechanical strength. The 50% Ni/SiO 2 catalyst is active as the 'A' catalyst but loses its activity after treatment at temperature > 600 C, its geometrical size shrinked. (authors). 25 refs., 25 figs., 36 tabs

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.

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Science.gov (United States)

Huang, Guan; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-01

This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O2. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

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

Science.gov (United States)

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

2017-08-30

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-02-15

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

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.

Sustainable fuel production by thermocatalytic decomposition of methane – A review

Directory of Open Access Journals (Sweden)

K. Srilatha

2017-12-01

Full Text Available Thermocatalytic Decomposition of Methane (TCD is a completely green single step technology for producing hydrogen and carbon nanomaterials. This paper review about the research in laboratory-scale on TCD, specifically the recent advances like co-feeding effect and regeneration of catalyst for enhancing the productivity of the entire process. Although a remarkable success on the laboratory-scale has been fulfilled, TCD for free greenhouse gas (GHG hydrogen production is still in its infancy. The necessity for commercialization of TCD is more than ever in the present-day condition of massive GHG emission. TCD generally studied over several types of catalysts, for example mono, bi, trimetallic, combination of metal–metal oxide, carbon and metal doped carbon catalysts. Catalyst Deactivation is the main problem found in TCD process. Regeneration of catalyst and co-feeding of methane with other hydrocarbon are the two main solutions placed helped in accordance to overcome deactivation problem. Higher amount of co-feed hydrocarbon in situ produce more amount of highly active carbon deposits which support further methane decomposition to produce extra hydrogen. The conversion rate of methane increases with increasing temperature and decreases with the flow rate in the co-feeding process in a comparable manner as observed in normal TCD. The presence of co-components in the post-reaction stream is an important challenge attempted in the co-feeding and regeneration. Keywords: Hydrogen, Catalysts, Thermocatalytic decomposition

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

DEFF Research Database (Denmark)

Petrushina, Irina; Bandur, Viktor; Bjerrum, Niels

2002-01-01

The electrochemical promotion of catalytic methane oxidation was studied using a (CH4,O-2,Ar), Pt\\polybenzimidazole (PBI)-H3PO4\\Pt,(H-2,Ar) fuel cell at 135degreesC. It has been found that C2H2, CO2, and water are the main oxidation products. Without polarization the yield of C2H2 was 0......, meaning that there was a maximum promotion effect at a polarization of -0.15 V, or 0.45 V catalyst potential vs. a hydrogen electrode (3.8% C2H2 yield). The catalytic rate enhancement ratio, r(C-2)/r(o)(C-2), at this maximum was 4.2. There was no C2H2 production at polarization greater than or equal to0.......9% and the yield of CO2 was 7.3%. This means that C-2 open-circuit selectivity was approximately 11%. Open-circuit voltage was around 0.6 V. It has been shown that the CH4 --> C2H2 catalytic reaction can be electrochemically promoted at negative polarization and exhibits a clear "volcano-type'' promotion behavior...

Hydrogenation of carbon monoxide over supported palladium catalysts

Energy Technology Data Exchange (ETDEWEB)

Fujimoto, K.; Hashimoto, H.; Kunugi, T.

1978-03-01

An alumina-supported 2% palladium catalyst had higher activity for carbon monoxide hydrogenation than a silica-supported 2% palladium catalyst, at 250/sup 0/-400/sup 0/C and 1 atm. The addition of lanthanum oxide or thorium oxide, but not of potassium oxide, to the silica-supported catalyst increased the conversion at 350/sup 0/C from 1.1% to 81.0% with a selectivity of 56.1% for methane, 1.4% for C/sub 2/ compounds, 0.1% for C/sub 3/ compounds, and 42.5% for carbon dioxide. Temperature-programed desorption of carbon monoxide in a hydrogen stream showed that of two desorption peaks observed for carbon monoxide, the one at higher temperature corresponded to the carbon monoxide species which hydrogenates to methane and that the area of this peak increased with increasing thorium content of the catalyst. Graphs, tables, and 12 references.

C-13 isotopic studies of the surface catalysed reactions of methane

International Nuclear Information System (INIS)

Long, M.A.; He, S.J.X.; Adebajo, M.

1997-01-01

The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

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

African Journals Online (AJOL)

Then, the different reaction conditions on this catalyst in a fluidized bed reactor ... In transient state experiments, methane feed without the presence of oxygen in the gas ... and the speed decrease, methane conversion decreases dramatically.

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

Indian Academy of Sciences (India)

SOURABH MISHRA

2017-09-27

Sep 27, 2017 ... ... in the Design and Development of Catalysts and their Applications ... of methane (natural gas) into transportable chemicals ... molybdenum (Mo) catalyst under non-oxidative condi- ... Micromeritics ASAP 2010 apparatus at liquid nitrogen tem- ... fixed-bed tubular reactor (500 mm length & 15 mm ID) at.

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.)

Methane synthesis under mild conditions for decentralized applications

International Nuclear Information System (INIS)

Schlueter, Michael; Roensch, Stefan

2016-01-01

It is a central aim of the German government to significantly reduce the emission of greenhouse gases in the next years. One possibility to reach this aim is the substitution of fossil fuels, especially natural gas, by fuels from biogenic sources (Bio-SNG). However, it is a drawback of Bio-SNG that the production costs are considerably higher than those of fossil natural gas. This work provides an approach to reduce the production costs of Bio-SNG. It is the aim to reduce the process parameters of the methane synthesis. At the same time, it has to be ensured that high methane yields are achieved even at those mild conditions. A procedure for the optimization of the methanation catalyst activity will be presented. If the catalyst is as active as possible even at mild conditions, it will be possible to produce Bio-SNG cost efficient even in small, decentralized scale.

The oxidative coupling of methane with cofeeding of ethane

NARCIS (Netherlands)

Chen, Q.; Couwenberg, P.M.; Marin, G.B.

1994-01-01

The oxidative coupling of methane with cofeeding of ethane was investigated experimentally both in the absence and in the presence of a Sn/Li/MgO catalyst. Cofeeding ethane in the absence of catalyst results in a higher total radical concentration, explaining the strong increase of the observed feed

Links between seawater flooding, soil ammonia oxidiser communities and their response to changes in salinity.

Science.gov (United States)

Nacke, Heiko; Schöning, Ingo; Schindler, Malte; Schrumpf, Marion; Daniel, Rolf; Nicol, Graeme W; Prosser, James I

2017-11-01

Coastal areas worldwide are challenged by climate change-associated increases in sea level and storm surge quantities that potentially lead to more frequent flooding of soil ecosystems. Currently, little is known of the effects of inundation events on microorganisms controlling nitrification in these ecosystems. The goal of this study was to investigate the impact of seawater flooding on the abundance, community composition and salinity tolerance of soil ammonia oxidisers. Topsoil was sampled from three islands flooded at different frequencies by the Wadden Sea. Archaeal ammonia oxidiser amoA genes were more abundant than their betaproteobacterial counterparts, and the distribution of archaeal and bacterial ammonia oxidiser amoA and 16S rRNA gene sequences significantly differed between the islands. The findings indicate selection of ammonia oxidiser phylotypes with greater tolerance to high salinity and slightly alkaline pH (e.g. Nitrosopumilus representatives) in frequently flooded soils. A cluster phylogenetically related to gammaproteobacterial ammonia oxidisers was detected in all samples analysed in this survey. Nevertheless, no gammaprotebacterial amoA genes could be amplified via PCR and only betaproteobacterial ammonia oxidisers were detected in enrichment cultures. A slurry-based experiment demonstrated the tolerance of both bacterial and archaeal ammonia oxidisers to a wide range of salinities (e.g. Wadden Sea water salinity) in soil naturally exposed to seawater at a high frequency. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Enhanced gasification of wood in the presence of mixed catalysts

Energy Technology Data Exchange (ETDEWEB)

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

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

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

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.

Catalytic combustion for the elimination of methane, BTEX and other VOC : IV

International Nuclear Information System (INIS)

Hayes, R.E.; Wanke, S.E.

2008-01-01

Options for volatile organic compound combustion include homogeneous combustion (flaring) or catalytic combustion involving a flameless combustion process that uses a solid catalyst to promote the combustion reaction. This presentation discussed relative reactivity testing for volatile organic compounds (VOCs) over commercial catalysts. Several commercial pad catalysts were tested, as well as other powders. The relative reactivity of methane as well as benzene, toluene, ethylbenzene, and xylene (BTEX) were investigated. The purpose of the project was to evaluate combustion of concentrated methane streams that contained BTEX compounds; evaluate catalytic combustion using a counter diffusive radiant heater; develop mathematical models for the reactor to enhance design and understanding; improve the catalyst for BTEX combustion; and target application-dehydrator units. Topics that were addressed in the presentation included methane and benzene conversion; catalytic radiant heaters; small industrial and commercial units; measured temperature distribution; fuel slippage, methane conversion; the effect of water and hydrocarbons; the effect of water-liquid injection; and water addition as vapour. Several observations were offered, including that high percentages of injected liquid water can reduce reactor operating temperature; combustion of BTEX remained highly efficient, however liquid injection could also cause temperature reductions and ultimately the reactor would extinguish; and pre-heating the feed can eliminate the temperature drop and pad wetness problem. It was concluded that BTEX compounds are reactive, and the technology appears promising. 19 figs

Catalytic combustion for the elimination of methane, BTEX and other VOC : IV

Energy Technology Data Exchange (ETDEWEB)

Hayes, R.E.; Wanke, S.E. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering

2008-07-01

Options for volatile organic compound combustion include homogeneous combustion (flaring) or catalytic combustion involving a flameless combustion process that uses a solid catalyst to promote the combustion reaction. This presentation discussed relative reactivity testing for volatile organic compounds (VOCs) over commercial catalysts. Several commercial pad catalysts were tested, as well as other powders. The relative reactivity of methane as well as benzene, toluene, ethylbenzene, and xylene (BTEX) were investigated. The purpose of the project was to evaluate combustion of concentrated methane streams that contained BTEX compounds; evaluate catalytic combustion using a counter diffusive radiant heater; develop mathematical models for the reactor to enhance design and understanding; improve the catalyst for BTEX combustion; and target application-dehydrator units. Topics that were addressed in the presentation included methane and benzene conversion; catalytic radiant heaters; small industrial and commercial units; measured temperature distribution; fuel slippage, methane conversion; the effect of water and hydrocarbons; the effect of water-liquid injection; and water addition as vapour. Several observations were offered, including that high percentages of injected liquid water can reduce reactor operating temperature; combustion of BTEX remained highly efficient, however liquid injection could also cause temperature reductions and ultimately the reactor would extinguish; and pre-heating the feed can eliminate the temperature drop and pad wetness problem. It was concluded that BTEX compounds are reactive, and the technology appears promising. 19 figs.

Antioxidative activity and emulsifying properties of cuttlefish skin gelatin modified by oxidised phenolic compounds

NARCIS (Netherlands)

Aewsiri, T.; Benjakul, S.; Visessanguan, W.; Eun, J.B.; Wierenga, P.A.; Gruppen, H.

2009-01-01

Antioxidative activity and emulsifying properties of cuttlefish skin gelatin modified by different oxidised phenolic compounds including caffeic acid, ferulic acid and tannic acid at different concentrations were investigated. Oxidised phenolic compounds were covalently attached to gelatin as

Theoretical investigation of the mechanism of tritiated methane dehydrogenation reaction using nickel-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Dong, Liang; Li, Jiamao; Deng, Bing; Yang, Yong; Wang, Heyi [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Tan, Zhaoyi, E-mail: tanzhaoyi@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

2015-06-15

Graphical abstract: - Highlights: • Four-step dehydrogenation of CT{sub 4} catalyzed by Ni to form Ni–C by releasing T{sub 2}. • The process of Ni + CT{sub 4} → NiCT{sub 2} + T{sub 2} is more achievable than that of NiCT{sub 2} → NiC + T{sub 2}. • TNiCT → T{sub 2}NiC step is the RDS with the rate constant of k = 2.8 × 10{sup 13} exp(−313,136/RT). • The hydrogen isotope effect value of k{sub H}/k{sub T} is 2.94, and k{sub D}/k{sub T} is 1.39. • CH{sub 4} and CD{sub 4} dehydrogenations are likely to occur, accompanied by the CT{sub 4} cracking. - Abstract: The mechanism of tritiated methane dehydrogenation reaction catalyzed by nickel-based catalyst was investigated in detail by density functional theory (DFT) at the B3LYP/[6-311++G(d, p), SDD] level. The computational results indicated that the dehydrogenation of tritiated methane is endothermic. The decomposition of tritiated methane catalyzed by Ni to form Ni-based carbon (Ni–C) after a four-step dehydrogenation companied with releasing tritium. After the first and second dehydrogenation steps, Ni + CT{sub 4} formed NiCT{sub 2}. After the third and fourth dehydrogenation steps, NiCT{sub 2} formed NiC. The first and second steps of dehydrogenation occurred on both the singlet and triplet states, and the lowest energy route is Ni + CT{sub 4} → {sup 1}COM → {sup 1}TS1 → {sup 3}IM1 → {sup 3}TS2 → {sup 3}IM2. The third and fourth steps of dehydrogenation occurred on both the singlet and quintet states, and the minimum energy reaction pathway appeared to be IM3 → {sup 1}TS4 → {sup 5}IM4 → {sup 5}TS5 → {sup 5}IM5 → {sup 5}pro + T{sub 2}. The fourth step of dehydrogenation TNiCT → T{sub 2}NiC was the rate-determining step of the entire reaction with the rate constant of k{sub 2} = 2.8 × 10{sup 13} exp(−313,136/RT) (in cm{sup 3} mol{sup −1} s{sup −1}), and its activation energy barrier was calculated to be 51.8 kcal/mol. The Ni-catalyzed CH{sub 4} and CD{sub 4} cracking

Methane activation on palladium and mercury loaded solid supports

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

Methane activation on palladium and mercury loaded solid supports

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-31

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

Methanation of CO2 over Zeolite-Encapsulated Nickel Nanoparticles

DEFF Research Database (Denmark)

Goodarzi, Farnoosh; Kang, Liqun; Wang, Feng Ryan

2018-01-01

in an increased metal dispersion and, consequently, a high catalytic activity for CO2 methanation. With a gas hourly space velocity of 60000 ml/g catalyst h-1 and H2/CO2=4, the zeolite-encapsulated Ni nanoparticles result in 60% conversion at 450°C, which corresponds to a site-time yield of around 304 mol CH4/mol......Efficient methanation of CO2 relies on the development of more selective and stable heterogeneous catalysts. Here we present a simple and effective method to encapsulate Ni nanoparticles in zeolite silicalite-1. In this method, the zeolite is modified by selective desilication, which creates intra...

Biomimetic and Bioinspired Synthesis of Nanomaterials/Nanostructures.

Science.gov (United States)

Zan, Guangtao; Wu, Qingsheng

2016-03-16

In recent years, due to its unparalleled advantages, the biomimetic and bioinspired synthesis of nanomaterials/nanostructures has drawn increasing interest and attention. Generally, biomimetic synthesis can be conducted either by mimicking the functions of natural materials/structures or by mimicking the biological processes that organisms employ to produce substances or materials. Biomimetic synthesis is therefore divided here into "functional biomimetic synthesis" and "process biomimetic synthesis". Process biomimetic synthesis is the focus of this review. First, the above two terms are defined and their relationship is discussed. Next different levels of biological processes that can be used for process biomimetic synthesis are compiled. Then the current progress of process biomimetic synthesis is systematically summarized and reviewed from the following five perspectives: i) elementary biomimetic system via biomass templates, ii) high-level biomimetic system via soft/hard-combined films, iii) intelligent biomimetic systems via liquid membranes, iv) living-organism biomimetic systems, and v) macromolecular bioinspired systems. Moreover, for these five biomimetic systems, the synthesis procedures, basic principles, and relationships are discussed, and the challenges that are encountered and directions for further development are considered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

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  |  

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)

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

NARCIS (Netherlands)

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

1989-01-01

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

OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

Energy Technology Data Exchange (ETDEWEB)

Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

1998-04-01

The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

Process and catalysts for the gasification of methanol. [German Patent

Energy Technology Data Exchange (ETDEWEB)

Harris, N.; Dennis, A.J.; Shevels, T.F.

1975-02-13

The invention concerns catalysts and catalytic processes for the gasification of methanol which is used to manufacture methane from methanol. Mixtures of iron and chromium oxide, phosphate, phosphoric acid, tungstate, tungstic acid, aluminium phosphate, aluminium oxide are suitable as dehydrating catalysts. Gasification takes place together with steam and dehydrogenating catalysts at high temperature. The molar ratios steam: methanol are described.

Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

Science.gov (United States)

Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

2013-01-01

Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

Coatings of active and heat-resistant cobalt-aluminium xerogel catalysts.

Science.gov (United States)

Schubert, Miriam; Schubert, Lennart; Thomé, Andreas; Kiewidt, Lars; Rosebrock, Christopher; Thöming, Jorg; Roessner, Frank; Bäumer, Marcus

2016-09-01

The application of catalytically coated metallic foams in catalytic processes has a high potential for exothermic catalytic reactions such as CO2 methanation or Fischer-Tropsch synthesis due to good heat conductivity, improved turbulent flow properties and high catalyst efficiencies. But the preparation of homogenous catalyst coats without pore blocking is challenging with conventional wash coating techniques. Here, we report on a stable and additive free colloidal CoAlOOH suspension (sol) for the preparation of catalytically active Co/Al2O3 xerogel catalysts and coatings. Powders with 18wt% Co3O4 prepared from this additive free synthesis route show a catalytic activity in Fischer-Tropsch synthesis and CO2 methanation which is similar to a catalyst prepared by incipient wetness impregnation (IWI) after activating the material under flowing hydrogen at 430°C. Yet, the xerogel catalyst exhibits a much higher thermal stability as compared to the IWI catalyst, as demonstrated in catalytic tests after different heat agings between 430°C and 580°C. It was also found that the addition of polyethylene glycol (PEG) to the sol influences the catalytic properties of the formed xerogels negatively. Only non-reducible cobalt spinels were formed from a CoAlOOH sol with 20wt% PEG. Metallic foams with pores sizes between 450 and 1200μm were coated with the additive free CoAlOOH sol, which resulted in homogenous xerogel layers. First catalytic tests of the coated metal foams (1200μm) showed good performance in CO2 methanation. Copyright © 2016 Elsevier Inc. All rights reserved.

Co-Aromatization of Methane with Olefins: The Role of Inner Pore and External Surface Catalytic Sites

Energy Technology Data Exchange (ETDEWEB)

Yung, Matthew M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); He, Peng [University of Calgary; Jarvis, Jack [University of Calgary; Meng, Shijun [University of Calgary; Wang, Aiguo [University of Calgary; Kou, Shiyu [University of Calgary; Gatip, Richard [University of Calgary; Liu, Lijia [Soochow University; Song, Hua [University of Calgary

2018-04-22

The co-aromatization of methane with olefins is investigated using Ag-Ga/HZSM-5 as the catalyst at 400 degrees C. The presence of methane has a pronounced effect on the product distribution in terms of increased average carbon number and substitution index and decreased aromatic carbon fraction compared with its N2 environment counterpart. The participation of methane during the co-aromatization over the Ag-Ga/HZSM-5 catalyst diminishes as the co-fed olefin feedstock molecule becomes larger, from 1-hexene to 1-octene and 1-decene, in diameter. The effect of suppressed methane participation with larger olefinic molecules is not as significant when Ag-Ga/HY is employed as the catalyst, which might be attributed to the larger pore size of HY that gives more room to hold olefin and methane molecules within the inner pores and reduces the diffusion limitation of olefin molecules. The effect of olefin feedstock on the methane participation during the co-aromatization over Ag-Ga/HZSM-5 is experimentally evidenced by 13C and 2D NMR. The incorporation of the methane carbon atoms into the phenyl ring of product molecules is reduced significantly with larger co-fed olefins, whereas its incorporation into the substitution groups of the formed aromatic molecules is not notably affected, suggesting that the methane participation in the phenyl ring formation might preferably occur within inner pores, while its incorporation into substitution groups may mainly take place on external catalytic sites. This hypothesis is well supported by the product selectivity obtained over Ag-Ga/HZSM-5 catalysts prepared using conventional ZSM-5, ZSM-5 with the external catalytic sites deactivated, nanosize ZSM-5, ZSM-5 with a micro/meso pore structure and ZSM-5 with the inner pores blocked, and further confirmed by the isotopic labeling studies.

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

DEFF Research Database (Denmark)

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

2009-01-01

The dynamics of the ignition and extinction of the catalytic partial oxidation (CPO) of methane to hydrogen and carbon monoxide over Pt-Rh/Al2O3 and Pt/Al2O3 were studied in the subsecond timescale using quick-EXAFS with a novel cam-driven X-ray monochromator employing Si(111) and Si(311) crystals...... to discuss the potential and limitation of this technique in catalysis and related areas. With respect to the noble metal catalysed partial oxidation of methane, several interesting observations were made: structural changes during ignition were-independent of the chosen reaction conditions......-significantly faster than during the extinction of the reaction. The dynamic behavior of the catalysts was dependent on the flow conditions and the respective noble metal component(s). Higher reaction gas flow led to a faster ignition process. While the ignition over Pt-Rh/Al2O3 occurred at lower temperature than over...

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

Microchannel Methanation Reactors Using Nanofabricated Catalysts, Phase II

Data.gov (United States)

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

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.

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.

Autothermal catalytic pyrolysis of methane as a new route to hydrogen production with reduced CO{sub 2} emissions

Energy Technology Data Exchange (ETDEWEB)

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

2006-08-15

Hydrogen production plants are among major sources of CO{sub 2} emissions into the atmosphere. The objective of this paper is to explore new routes to hydrogen production from natural gas (or methane) with drastically reduced CO{sub 2} emissions. One approach analyzed in this paper is based on thermocatalytic decomposition (or pyrolysis) of methane into hydrogen gas and elemental carbon over carbon-based catalysts. Several heat input options to the endothermic process are discussed in the paper. The authors conduct thermodynamic analysis of methane decomposition in the presence of small amounts of oxygen in an autothermal (or thermo-neutral) regime using AspenPlus(TM) chemical process simulator. Methane conversion, products yield, effluent gas composition, process enthalpy flows as a function of temperature, pressure and O{sub 2}/CH{sub 4} ratio has been determined. CO{sub 2} emissions (per m{sup 3} of H{sub 2} produced) from the process could potentially be a factor of 3-5 less than from conventional hydrogen production processes. Oxygen-assisted decomposition of methane over activated carbon (AC) and AC-supported iron catalysts over wide range of temperatures and O{sub 2}/CH{sub 4} ratios was experimentally verified. Problems associated with the catalyst deactivation and the effect of iron doping on the catalyst stability are discussed. (author)

An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

Science.gov (United States)

Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

2013-01-01

Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

Reduction of a Ni/Spinel Catalyst for Methane Reforming

DEFF Research Database (Denmark)

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

2015-01-01

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

Biomimetic Flow Sensors

NARCIS (Netherlands)

Casas, J.; Liu, Chang; Krijnen, Gijsbertus J.M.

2012-01-01

Biomimetic flow sensors are biologically inspired devices that measure the speed and direction of fluids. This survey starts by describing the role and functioning of airflow-sensing hairs in arthropods and in fishes, carries on with the biomimetic MEMS implementations, both for air and water flow

Low-Energy, Low-Cost Production of Ethylene by Low- Temperature Oxidative Coupling of Methane

Energy Technology Data Exchange (ETDEWEB)

Radaelli, Guido [Siluria Technologies, Inc., San Francisco, CA (United States); Chachra, Gaurav [Siluria Technologies, Inc., San Francisco, CA (United States); Jonnavittula, Divya [Siluria Technologies, Inc., San Francisco, CA (United States)

2017-12-30

In this project, we develop a catalytic process technology for distributed small-scale production of ethylene by oxidative coupling of methane at low temperatures using an advanced catalyst. The Low Temperature Oxidative Coupling of Methane (LT-OCM) catalyst system is enabled by a novel chemical catalyst and process pioneered by Siluria, at private expense, over the last six years. Herein, we develop the LT-OCM catalyst system for distributed small-scale production of ethylene by identifying and addressing necessary process schemes, unit operations and process parameters that limit the economic viability and mass penetration of this technology to manufacture ethylene at small-scales. The output of this program is process concepts for small-scale LT-OCM catalyst based ethylene production, lab-scale verification of the novel unit operations adopted in the proposed concept, and an analysis to validate the feasibility of the proposed concepts.

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)

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.

Direct Aromaization of Methane

Energy Technology Data Exchange (ETDEWEB)

George Marcelin

1997-01-15

The thermal decomposition of methane offers significant potential as a means of producing higher unsaturated and aromatic hydrocarbons when the extent of reaction is limited. Work in the literature previous to this project had shown that cooling the product and reacting gases as the reaction proceeds would significantly reduce or eliminate the formation of solid carbon or heavier (Clo+) materials. This project studied the effect and optimization of the quenching process as a means of increasing the amount of value added products during the pyrolysis of methane. A reactor was designed to rapidly quench the free-radical combustion reaction so as to maximize the yield of aromatics. The use of free-radical generators and catalysts were studied as a means of lowering the reaction temperature. A lower reaction temperature would have the benefits of more rapid quenching as well as a more feasible commercial process due to savings realized in energy and material of construction costs. It was the goal of the project to identify promising routes from methane to higher hydrocarbons based on the pyrolysis of methane.

Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.

Science.gov (United States)

Largeron, Martine; Chiaroni, Angèle; Fleury, Maurice-Bernard

2008-01-01

Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.

From fundamental studies of reactivity on single crystals to the design of catalysts

Science.gov (United States)

H. Larsen, Jane; Chorkendorff, Ib

One of the prominent arguments for performing surface science studies have for many years been to improve and design new and better catalysts. Although surface science has provided the fundamental framework and tools for understanding heterogeneous catalysis until now there have been extremely few examples of actually designing new catalysts based solely on surface science studies. In this review, we shall demonstrate how a close collaboration between different fundamental disciplines like structural-, theoretical-and reactivity-studies of surfaces as well as a strong interaction with industry can have strong synergetic effects and how this was used to develop a new catalyst. As so often before the studies reviewed here were not initiated with the objective to solve a specific problem, but realizing that a new class of very stable two-dimensional alloys could be synthesized from otherwise immiscible metals made it possible to present a new solution to a specific problem in the industrial catalysis relating to methane activation in the steam reforming process. Methane is the main constituent of natural gas and it is an extremely important raw material for many large scale chemical processes such as production of hydrogen, ammonia, and methanol. In the steam reforming process methane and water are converted into a mixture of mainly hydrogen and carbon monoxide, the so-called synthesis gas. Industrially the steam reforming process usually takes place over a catalyst containing small nickel crystallites highly dispersed on a porous support material like aluminum/magnesium oxides in order to achieve a high active metal area. There is a general consensus that the rate limiting step of this process is the dissociative sticking of methane on the nickel surface. Driven by the desire to understand this step and hopefully be able to manipulate the reactivity, a large number of investigations of the methane/nickel interaction have been performed using nickel single crystals as

Effect of annealing temperature on the structure and coke-resistance of nickel–iron bimetallic catalytic layer for in situ methane steam reforming in SOFC operation

Energy Technology Data Exchange (ETDEWEB)

Liu, Xuehua; Zhang, Hanqing; Zhao, DanDan; Tang, Dian; Zhang, Teng, E-mail: teng_zhang@fzu.edu.cn

2014-11-15

Highlights: • An intermediate FeNi{sub 3} phase forms in all N{sub i0.75}Fe{sub 0.25} catalysts in present work. • The catalyst annealed at 705 °C has smallest calculated surface energy. • The catalyst annealed at 705 °C also exhibits the best coke resistance in methane. • The cell with catalyst layer annealed at 705 °C has the best stability in methane. - Abstract: In this paper, the effect on coke formation of adding a Ni{sub 0.75}Fe{sub 0.25} catalyst layer to the anode side of a fuel cell running on methane is investigated. The formation of an intermediate FeNi{sub 3} phase can be observed in catalysts annealed at different temperatures. The catalyst annealed at 705 °C has the smallest calculated surface energy and grain size among all catalysts annealed at different temperatures. In addition, the O{sub 2}-TPO profiles and Raman spectra of spent anode material reveal that the catalyst annealed at 705 °C has the best coke resistance among all catalysts. Moreover, the cell with catalyst layer annealed at 705 °C, under a current density of 600 mA cm{sup −2} at 650 °C, experiences a decrease of 10% after operating in methane for 260 min, which is much more stable than that without catalyst layer (a decrease of 50%)

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

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

Cerium Modified Pillared Montmorillonite Supported Cobalt Catalysts for Fischer Tropsch Synthesis

International Nuclear Information System (INIS)

Ahmad, N.; Ali, Z.; Abbas, S. M.; Hussain, F.

2015-01-01

Fischer-Tropsch (FT) synthesis was accomplished over Al-pillared Montmorillonite supported 20 wt% Co modified with different weight% of cerium catalysts. These catalysts were prepared by impregnation method while structural characterizations of the prepared samples were performed by XRD, TPR, NH/sub 3/TPD, TGA, BET, XRF and SEM techniques. The Fischer Tropsch reaction was studied in fixed bed micro catalytic reactor at temperature range of 220, 260 and 275 degree C and at different pressure (1, 5 and 10 bars). From the activity results, it was found that by pillaring NaMMT with Al higher catalytic activity and lower methane selectivity of NaMMT was achieved. Furthermore, the results of FT synthesis reaction revealed that cerium incorporation increased the dispersion of Co/sub 3/O/sub 4/ on the surface and consequently resulted in enhanced catalytic activity. Additionally, the C/sub 5/-C/sub 12/ hydrocarbons and methane selectivity increased while C/sub 22+/ hydrocarbons selectivity was decreased over cerium modified catalysts. Higher reaction temperature (>220 degree C) resulted in significant enhancement in CO conversion and methane selectivity. Though, increase in pressure from 1 to 10 bars eventually resulted in increase in C/sub 5+/ hydrocarbons and decrease in methane and C/sub 2/-C/sub 5/ hydrocarbons selectivity. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-12-31

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Biomimetics in drug delivery systems: A critical review.

Science.gov (United States)

Sheikhpour, Mojgan; Barani, Leila; Kasaeian, Alibakhsh

2017-05-10

Today, the advanced drug delivery systems have been focused on targeted drug delivery fields. The novel drug delivery is involved with the improvement of the capacity of drug loading in drug carriers, cellular uptake of drug carriers, and the sustained release of drugs within target cells. In this review, six groups of therapeutic drug carriers including biomimetic hydrogels, biomimetic micelles, biomimetic liposomes, biomimetic dendrimers, biomimetic polymeric carriers and biomimetic nanostructures, are studied. The subject takes advantage of the biomimetic methods of productions or the biomimetic techniques for the surface modifications, similar to what accrues in natural cells. Moreover, the effects of these biomimetic approaches for promoting the drug efficiency in targeted drug delivery are visible. The study demonstrates that the fabrication of biomimetic nanocomposite drug carriers could noticeably promote the efficiency of drugs in targeted drug delivery systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment of hydrothermal pretreatment of various lignocellulosic biomass with CO2 catalyst for enhanced methane and hydrogen production.

Science.gov (United States)

Eskicioglu, Cigdem; Monlau, Florian; Barakat, Abdellatif; Ferrer, Ivet; Kaparaju, Prasad; Trably, Eric; Carrère, Hélène

2017-09-01

Hydrothermal pretreatment of five lignocellulosic substrates (i.e. wheat straw, rice straw, biomass sorghum, corn stover and Douglas fir bark) were conducted in the presence of CO 2 as a catalyst. To maximize disintegration and conversion into bioenergy (methane and hydrogen), pretreatment temperatures and subsequent pressures varied with a range of 26-175 °C, and 25-102 bars, respectively. Among lignin, cellulose and hemicelluloses, hydrothermal pretreatment caused the highest reduction (23-42%) in hemicelluloses while delignification was limited to only 0-12%. These reductions in structural integrity resulted in 20-30% faster hydrolysis rates during anaerobic digestion for the pretreated substrates of straws, sorghum, and corn stover while Douglas fir bark yielded 172% faster hydrolysis/digestion due to its highly refractory nature in the control. Furans and phenolic compounds formed in the pretreated hydrolyzates were below the inhibitory levels for methane and hydrogen production which had a range of 98-340 ml CH 4 /g volatile solids (VS) and 5-26 ml H 2 /g VS, respectively. Results indicated that hydrothermal pretreatment is able to accelerate the rate of biodegradation without generating high levels of inhibitory compounds while showing no discernible effect on ultimate biodegradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Shining X-rays on catalysts at work

Energy Technology Data Exchange (ETDEWEB)

Grunwaldt, J-D, E-mail: jdg@kt.dtu.d [Technical University of Denmark, Department of Chemical and Biochemical Engineering, Building 229, DK-2800 Kgs. Lyngby (Denmark)

2009-11-15

Structure-performance relationships gained by studying catalysts at work are considered the key to further development of catalysts underlined here by a brief overview on our research in this area. The partial oxidation of methane to hydrogen and carbon monoxide over Pt- and Rh-based catalysts and the total combustion of hydrocarbons demonstrate the importance of structural identification of catalysts in its working state and the measurement of the catalytic performance at the same time. Moreover, proper cell design is a key both here and in liquid phase reactions including preparation or high pressure reactions. In several cases structural changes during preparation, activation and reaction occur on a subminute scale or the catalyst structure varies inside a reactor as a result of temperature or concentration gradients. This, additionally, requires time and spatial resolution. Examples from time-resolved QEXAFS studies during the partial oxidation of methane over Pt- and Rh-based catalysts demonstrate some of the recent developments of the technique (use not only of Si(111) but also Si(311) crystals, angular encoder, full EXAFS spectra at subsecond recording time, and modulation excitation spectroscopy). In order to obtain spectroscopic information on the oxidation state inside a microreactor, scanning and full field X-ray microscopy with X-ray absorption spectroscopic contrast were achieved under reaction conditions. If a microbeam is applied, fast scanning techniques like QEXAFS are required. In this way, even X-ray absorption spectroscopic tomographic images of a slice of a microreactor were obtained. The studies were recently extended to spatiotemporal studies that give important insight into the dynamics of the catalyst structure in a spatial manner with subsecond time-resolution.

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.

Oxidised fish oil does not influence established markers of oxidative stress in healthy human subjects

DEFF Research Database (Denmark)

Ottestad, Inger; Vogt, Gjermund; Retterstøl, Kjetil

2012-01-01

markers of oxidative stress, lipid peroxidation and inflammation, and the level of plasma n-3 FA after intake of oxidised fish oil. In a double-blinded randomised controlled study, healthy subjects (aged 18–50 years, n 54) were assigned into one of three groups receiving capsules containing either 8 g...... difference was observed between the fish oil groups. No changes in a variety of in vivo markers of oxidative stress, lipid peroxidation or inflammation were observed after daily intake of oxidised fish oil for 3 or 7 weeks, indicating that intake of oxidised fish oil may not have unfavourable short......-term effects in healthy human subjects....

Biomimetic architectures by plasma processing fabrication and applications

CERN Document Server

Chattopadhyay, Surojit

2014-01-01

Photonic structures in the animal kingdom: valuable inspirations for bio-mimetic applications. Moth eye-type anti-reflecting nanostructures by an electron cyclotron resonance plasma. Plasma-processed biomimetic nano/microstructures. Wetting properties of natural and plasma processed biomimetic surfaces. Biomimetic superhydrophobic surface by plasma processing. Biomimetic interfaces of plasma modified titanium alloy.

Mechanism-Based Design of Green Oxidation Catalysts

Energy Technology Data Exchange (ETDEWEB)

Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

2015-03-16

In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this

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.

Cardiovascular risk assessment with oxidised LDL measurement in postmenopausal women receiving intranasal estrogen replacement therapy.

Science.gov (United States)

Kurdoglu, Mertihan; Yildirim, Mulazim; Kurdoglu, Zehra; Erdem, Ahmet; Erdem, Mehmet; Bilgihan, Ayse; Goktas, Bulent

2011-08-01

To investigate the effect of intranasal estrogen replacement therapy administered to postmenopausal women alone or in combination with progesterone on markers of cardiovascular risk. The study was conducted with 44 voluntary postmenopausal women. In group I (n = 15), the patients were treated with only intranasal estradiol (300 μg/day estradiol hemihydrate). In group II (n = 11), the patients received cyclic progesterone (200 mg/day micronized progesterone) for 12 days in each cycle in addition to continuous intranasal estradiol. Group III (n = 18) was the controls. Serum lipid profiles, oxidised low-density lipoprotein (LDL) and other markers of cardiovascular risk were assessed at baseline and at the 3rd month of the treatment. Lipid profile, LDL apolipoprotein B, lipoprotein a, homocysteine, oxidised LDL values and oxidised LDL/LDL cholesterol ratio were not observed to change after 3 months compared to baseline values within each group (p > 0.016). In comparison to changes between the groups after the treatment, only oxidised LDL levels and oxidised LDL/LDL cholesterol ratios of group II were increased compared to control group (p < 0.05). Intranasal estradiol alone did not appear to have an effect on markers of cardiovascular risk in healthy postmenopausal women. However, the addition of cyclic oral micronized progesterone to intranasal estradiol influenced the markers of cardiovascular risk negatively in comparison to non-users in healthy postmenopausal women.

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.

Advances in the Partial Oxidation of Methane to Synthesis Gas

Institute of Scientific and Technical Information of China (English)

Quanli Zhu; Xutao Zhao; Youquan Deng

2004-01-01

The conversion and utilization of natural gas is of significant meaning to the national economy,even to the everyday life of people. However, it has not become a popular industrial process as expected due to the technical obstacles. In the past decades, much investigation into the conversion of methane,predominant component of natural gas, has been carried out. Among the possible routes of methane conversion, the partial oxidation of methane to synthesis gas is considered as an effective and economically feasible one. In this article, a brief review of recent studies on the mechanism of the partial oxidation of methane to synthesis gas together with catalyst development is wherein presented.

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

The kinetics of steam-carbon dioxide conversion, rational ways and production catalysts of process gas

International Nuclear Information System (INIS)

Khamroev, F.B.

2016-01-01

The purpose of the present work is to study the kinetics of steam-carbon dioxide conversion, rational ways and production catalysts of process gas. The experimental equation of steam-carbon methane conversion, heat stability increasing and catalyst efficiency, decreasing of hydrodynamical resistance of catalyst layer were determined.

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.

Silica Supported Platinum Catalysts for Total Oxidation of the Polyaromatic Hydrocarbon Naphthalene: An Investigation of Metal Loading and Calcination Temperature

Directory of Open Access Journals (Sweden)

David R. Sellick

2015-04-01

Full Text Available A range of catalysts comprising of platinum supported on silica, prepared by an impregnation method, have been studied for the total oxidation of naphthalene, which is a representative Polycyclic Aromatic Hydrocarbon. The influence of platinum loading and calcination temperature on oxidation activity was evaluated. Increasing the platinum loading up to 2.5 wt.% increased the catalyst activity, whilst a 5.0 wt.% catalyst was slightly less active. The catalyst containing the optimum 2.5 wt.% loading was most active after calcination in air at 550 °C. Characterisation by carbon monoxide chemisorption and X-ray photoelectron spectroscopy showed that low platinum dispersion to form large platinum particles, in combination with platinum in metallic and oxidised states was important for high catalyst activity. Catalyst performance improved after initial use in repeat cycles, whilst there was slight deactivation after prolonged time-on-stream.

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.

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....

Biomimetic thin film synthesis

Energy Technology Data Exchange (ETDEWEB)

Graff, G.L.; Campbell, A.A.; Gordon, N.R.

1995-05-01

The purpose of this program is to develop a new process for forming thin film coatings and to demonstrate that the biomimetic thin film technology developed at PNL is useful for industrial applications. In the biomimetic process, mineral deposition from aqueous solution is controlled by organic functional groups attached to the underlying substrate surface. The coatings process is simple, benign, inexpensive, energy efficient, and particularly suited for temperature sensitive substrate materials (such as polymers). In addition, biomimetic thin films can be deposited uniformly on complex shaped and porous substrates providing a unique capability over more traditional line-of-sight methods.

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

Biomimetic and microbial approaches to solar fuel generation.

Science.gov (United States)

Magnuson, Ann; Anderlund, Magnus; Johansson, Olof; Lindblad, Peter; Lomoth, Reiner; Polivka, Tomas; Ott, Sascha; Stensjö, Karin; Styring, Stenbjörn; Sundström, Villy; Hammarström, Leif

2009-12-21

Photosynthesis is performed by a multitude of organisms, but in nearly all cases, it is variations on a common theme: absorption of light followed by energy transfer to a reaction center where charge separation takes place. This initial form of chemical energy is stabilized by the biosynthesis of carbohydrates. To produce these energy-rich products, a substrate is needed that feeds in reductive equivalents. When photosynthetic microorganisms learned to use water as a substrate some 2 billion years ago, a fundamental barrier against unlimited use of solar energy was overcome. The possibility of solar energy use has inspired researchers to construct artificial photosynthetic systems that show analogy to parts of the intricate molecular machinery of photosynthesis. Recent years have seen a reorientation of efforts toward creating integrated light-to-fuel systems that can use solar energy for direct synthesis of energy-rich compounds, so-called solar fuels. Sustainable production of solar fuels is a long awaited development that promises extensive solar energy use combined with long-term storage. The stoichiometry of water splitting into molecular oxygen, protons, and electrons is deceptively simple; achieving it by chemical catalysis has proven remarkably difficult. The reaction center Photosystem II couples light-induced charge separation to an efficient molecular water-splitting catalyst, a Mn(4)Ca complex, and is thus an important template for biomimetic chemistry. In our aims to design biomimetic manganese complexes for light-driven water oxidation, we link photosensitizers and charge-separation motifs to potential catalysts in supramolecular assemblies. In photosynthesis, production of carbohydrates demands the delivery of multiple reducing equivalents to CO(2). In contrast, the two-electron reduction of protons to molecular hydrogen is much less demanding. Virtually all microorganisms have enzymes called hydrogenases that convert protons to hydrogen, many of

ETHANOL OXIDATION OVER AU/TIO2 CATALYSTS

African Journals Online (AJOL)

DR. AMINU

The adsorption and reaction of ethanol over Au/TiO2 catalysts was investigated using pulse ... the surface disappears, so the mechanism reverts to a decomposition pathway, producing methane, ... allowed to flow at a rate of 30 ml per minutes.

Soot oxidation over NOx storage catalysts. Activity and deactivation

International Nuclear Information System (INIS)

Krishna, K.; Makkee, M.

2006-01-01

Soot oxidation activity and deactivation of NO x storage and reduction (NSR) catalysts containing Pt, K, and Ba supported on Al 2 O 3 , are studied under a variety of reaction conditions. K-containing catalysts decrease soot oxidation temperature with O 2 alone and the presence of Pt further enhance the activity due to synergetic effect. The active species responsible for synergism on Pt/K-Al 2 O 3 are unstable and cannot be regenerated. Soot oxidation temperature decreases by about 150 o C with NO+O 2 exhaust feed gas and under lean conditions NSR system acts as catalysed soot filter (CSF). The reactions that are mainly responsible for decreasing soot oxidation temperature are: (1) soot oxidation with NO 2 followed by NO recycles to NO 2 , and (2) soot oxidation with O 2 assisted by NO 2 . Only a part of the stored NO x that is decomposed at high temperatures under lean conditions is found to be useful for soot oxidation. NO x storage capacity of NSR catalysts decreases upon ageing under soot oxidising conditions. This will lead to a decreased soot oxidation activity on stored nitrate decomposition. Pt/K-Al 2 O 3 catalyst is more active, but least stable compared with Pt/Ba-Al 2 O 3 . (author)

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.

Highly cost-effective and sulfur/coking resistant VOx-grafted TiO2 nanoparticles as an efficient anode catalyst for direct conversion of dry sour methane in solid oxide fuel cells

NARCIS (Netherlands)

Garcia, A.; Yan, N.; Vincent, A.; Singh, A.; Hill, J.M.; Chuang, K. T.; Luo, J.L.

2015-01-01

In this work, we show that grafted metal oxide can be a highly cost-effective and active anode for solid oxide fuel cells for sour methane conversion. The developed electro-catalyst was composed of vanadium oxide grafted TiO2 nanoparticles (VOx/TiO2) infiltrated into a porous La0.4Sr0.5Ba0.1TiO3+δ

High-BTU gas production from tar-bearing hot coke oven gas over iron catalyst

Energy Technology Data Exchange (ETDEWEB)

L.Y. Li; K. Morishita; T. Takarada [Gunma University, Gunma (Japan). Department of Biological and Chemical Engineering

2005-07-01

To utilize the tar-bearing hot coke oven gas (the by-product of coke making process) more effectively, a process was developed by converting the hot coke oven gas into a methane rich high-BTU gas over iron-bearing catalysts. The catalytic behaviour of Indonesian limonite ore was mainly discussed. For a reference, a conventional nickel catalyst (Ni/Al{sub 2}O{sub 3}) was employed. Laboratory scale tests were carried out in a two-stage fixed-bed reactor at ambient pressure. A bituminous coal sample was heated at first stage, the volatiles was carried by feed gas and decomposed at second stage. The limonite promoted hydropyrolysis of coal volatiles similar to Ni/Al{sub 2}O{sub 3} catalyst. High yields of total product gas and methane were obtained at 50 vol.% hydrogen atmosphere with a feed gas of 60 ml min{sup -1} hydrogen and 60 ml min{sup -1} nitrogen. After experiments, hydrocarbons heavier than ethane were not observed. Also that, carbon balance was more than 99.8% in coal char, product gases and carbon deposits. It was considered that coal volatiles converted into light gases and carbon almost completely in catalyst bed. Yields of product gas and methane depended upon catalytic temperature. At 923 K, the maximum yield of product gas was achieved at 74.3% for limonite catalyst on carbon balance with methane 83.2 vol.% of the carbonaceous gas products. Comparing with limonite, Fe/Al{sub 2}O{sub 3} and BOF dust samples showed low activities on coal volatiles catalytic decomposition. 21 refs., 5 figs., 3 tabs.

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

International Nuclear Information System (INIS)

Engelmann Pirez, M.

2004-12-01

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

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

KAUST Repository

Al-Sabban, Bedour E.

2016-01-01

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

Process for producing ethane and/or ethylene from methane. Verfahren zur Herstellung von Ethan und bzw. oder Ethylen aus Methan

Energy Technology Data Exchange (ETDEWEB)

Baerns, M.; Hinsen, W.

1984-04-12

According to the invention, methane is converted into hydrocarbons with oxygen with high selectivity. This is done in the presence of a catalyst fluidized in a fluidized bed - preferably lead oxide or a mixture of this with antimony oxide - at temperatures between 600 and 800/sup 0/C and at oxygen partial pressures preferably below 0.1-0.2 bar. The ratio of methane partial pressure to oxygen partial pressure should be greater than 2 to 5 if possible. The reactor is operated with gas feedback, in order to raise the selectivity even more.

Biomimetics

Indian Academy of Sciences (India)

M. Senthilkumar (Newgen Imaging) 1461 1996 Oct 15 13:05:22

Biomimetics is the field of scientific endeavour, which attempts to design systems and syn- thesise materials through ... natural systems with a view to achieve analogous synthetic design and manufacture. On the ..... Industrial production.

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...

A transient kinetic study of nickel-catalyzed methanation: Final report

International Nuclear Information System (INIS)

Hoost, T.E.; Goodwin, J.G. Jr.

1988-11-01

The results of this study are in two major parts. In Part I the use of steady-state isotopic transients of multiple elements (C, H, and O) under actual methanation reaction conditions has permitted an assessment of the reactivity of water on a Ni powder catalyst. It was concluded based on the addition of isotopic water that oxygen, once reacted to form water, is able to readsorb even where the surface coverage of CO remains high. At the low relative partial pressures of water used, however, there was no effect of added water on the formation of methane. The surface residence time of water determined from isotopic transients contains the residence time on the surface during the primary formation reaction as well as the time spent during readsorption(s). Part II addressed how a catalyst modifier (in this case Cl) affects methanation in CO hydrogenation using steady-state isotopic transient kinetic analysis (SSITKA) of methanation. The results obtained using silica-supported Ru suggest the structural rearrangements induced by the presence of chlorine, rather than selective site blocking or electronic interactions, may be the primary mechanism of chlorine modification of the catalytic properties of supported metals for CO hydrogenation. SSITKA indicated that the decrease in methanation activity with increasing initial Cl concentration was a function of a decrease in the number of reactive surface intermediates (or sites) and not of a change in site activity. 36 refs., 10 figs., 5 tabs

Activity and selectivity control through periodic composition forcing over Fischer-Tropsch catalysts

Energy Technology Data Exchange (ETDEWEB)

Silveston, P L; Hudgins, R R; Adesina, A A; Ross, G S; Feimer, J L

1986-01-01

Data collected under steady-state and periodic composition forcing of the Fischer-Tropsch synthesis over three commonly used catalysts demonstrate that both activity and selectivity can be changed by the latter operating mode. Synthesis of hydrocarbons up to C/sub 7/are favored at the expense of the higher carbon numbers for the Co catalyst, while for the Ru catalyst, only the C/sub 3/ and lower species are favored. Only methane production is stimulated with the Fe catalyst. Fe and Ru catalysts shift production from alkenes to alkanes. Transient data is interpreted in the paper.

Biomimetic nanoparticles for inflammation targeting

Directory of Open Access Journals (Sweden)

Kai Jin

2018-01-01

Full Text Available There have been many recent exciting developments in biomimetic nanoparticles for biomedical applications. Inflammation, a protective response involving immune cells, blood vessels, and molecular mediators directed against harmful stimuli, is closely associated with many human diseases. As a result, biomimetic nanoparticles mimicking immune cells can help achieve molecular imaging and precise drug delivery to these inflammatory sites. This review is focused on inflammation-targeting biomimetic nanoparticles and will provide an in-depth look at the design of these nanoparticles to maximize their benefits for disease diagnosis and treatment.

Embedded SMA wire actuated biomimetic fin: a module for biomimetic underwater propulsion

International Nuclear Information System (INIS)

Wang Zhenlong; Hang Guanrong; Wang Yangwei; Li Jian; Du Wei

2008-01-01

An embedded shape memory alloy (SMA) wire actuated biomimetic fin is presented, and based on this module for biomimetic underwater propulsion, a micro robot fish (146 mm in length, 30 g in weight) and a robot squid (242 mm in length, 360 g in weight) were developed. Fish swim by undulating their body and/or fins. Squid and cuttlefish can also swim by undulating their fins. To simplify engineering modeling, the undulating swimming movement is assumed to be the integration of the movements of many flexible bending segments connected in parallel or in series. According to this idea, a biomimetic fin which can bend flexibly was developed. The musculature of a cuttlefish fin was investigated to aid the design of the biomimetic fin. SMA wires act as 'muscle fibers' to drive the biomimetic fin just like the transverse muscles of the cuttlefish fin. During the bending phase, elastic energy is stored in the elastic substrate and skin, and during the return phase, elastic energy is released to power the return movement. Theorem analysis of the bending angle was performed to estimate the bending performance of the biomimetic fin. Experiments were carried out on single-face fins with latex rubber skin and silicone skin (SF-L and SF-S) to compare the bending angle, return time, elastic energy storage and reliability. Silicone was found to be the better skin. A dual-face fin with silicone skin (DF-S) was tested in water to evaluate the actuating performance and to validate the reliability. Thermal analysis of the SMA temperature was performed to aid the control strategy. The micro robot fish and robot squid employ one and ten DF-S, respectively. Swimming experiments with different actuation frequencies were carried out. The speed and steering radius of the micro robot fish reached 112 mm s −1 and 136 mm, respectively, and the speed and rotary speed of the robot squid reached 40 mm s −1 and 22° s −1 , 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)

Creep rupture properties of oxidised 20%Cr austenitic stainless steels

International Nuclear Information System (INIS)

Lobb, R.C.; Ecob, R.C.

1989-02-01

Sheet specimens of stabilised 20%Cr/25%Ni/Nb and nitrided 20%Cr/25%Ni/Ti stainless steels, both used as fuel cladding materials in CAGRs, have been oxidised in simulated reactor gas (Co 2 /1-2%CO) for up to l.9kh at 850 0 C, including intermediate thermal cycles to room temperature. The oxidised specimens have been creep tested subsequently at 750 0 C, under conditions of constant stress. The creep rupture properties are affected differently for the two materials. For 20%Cr/25%Ni/Nb stainless steel, there was no effect of oxidation on the intrinsic microstructure, when compared with thermally aged, non-oxidised material. Any differences in creep ductility were ascribed to geometric effects in specimens of this alloy. Lower ductilities were associated with an increased incidence of pitting attack (higher oxide spallation) and it was concluded that the extent of local, rather than general, loss of section controlled the ductility. For nitrided 20%Cr/25%Ni/Ti stainless steel, the intrinsic microstructure was affected by oxidation, such that increased grain boundary precipitation of M 23 C 6 occurred. The resultant effect was for a greater tendency for intergranular failure at lower ductility than for the thermally aged material. The magnitude of this reduction could not be quantified because the specimen geometry was also changed by oxidation. In this instance, the oxidation mode that produced the most severe loss of section was grain boundary, rather than pitting, attack. This mode of attack was not linked directly to oxide fracture/spallation, but to the period of oxidation. (author)

Use of ionic liquids as coordination ligands for organometallic catalysts

Science.gov (United States)

Li, Zaiwei [Moreno Valley, CA; Tang, Yongchun [Walnut, CA; Cheng,; Jihong, [Arcadia, CA

2009-11-10

Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

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.

Biomimetics: determining engineering opportunities from nature

Science.gov (United States)

Fish, Frank E.

2009-08-01

The biomimetic approach seeks to incorporate designs based on biological organisms into engineered technologies. Biomimetics can be used to engineer machines that emulate the performance of organisms, particularly in instances where the organism's performance exceeds current mechanical technology or provides new directions to solve existing problems. For biologists, an adaptationist program has allowed for the identification of novel features of organisms based on engineering principles; whereas for engineers, identification of such novel features is necessary to exploit them for biomimetic development. Adaptations (leading edge tubercles to passively modify flow and high efficiency oscillatory propulsive systems) from marine animals demonstrate potential utility in the development of biomimetic products. Nature retains a store of untouched knowledge, which would be beneficial in advancing technology.

Adsorption and methanation of carbon dioxide on a nickel/silica catalyst

Energy Technology Data Exchange (ETDEWEB)

Falconer, J.L.; Zagli, A.E.

1980-04-01

Temperature-programed desorption and reaction studies showed that increasing amounts of CO/sub 2/ adsorbed on silica-supported 6.9% nickel with increasing temperature to a maximum adsorption at approx. 443/sup 0/K, i.e., that the adsorption was activated; that CO/sub 2/ desorbed partly as CO/sub 2/ with the peak at 543/sup 0/K, and partly as CO with several peaks; that in the presence of hydrogen, nearly all adsorbed CO/sub 2/ desorbed as methane, and a small amount as CO; and that the methane desorption peaks from adsorbed CO and CO/sub 2/ both occurred at 473/sup 0/K. These results suggested that carbon dioxide adsorbed dissociatively as a carbon monoxide and an oxygen species. An observed absence of higher hydrocarbons in the methanation products of carbon dioxide was attributed to a high hydrogen/carbon monoxide surface ratio caused by the activated carbon dioxide adsorption.

Oscillatory behaviour of catalytic properties, structure and temperature during the catalytic partial oxidation of methane on Pd/Al2O3

DEFF Research Database (Denmark)

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

2010-01-01

Pd/Al2O3 catalysts showed an oscillatory behaviour during the catalytic partial oxidation (CPO) of methane, which was investigated simultaneously by IR-thermography, X-ray absorption spectroscopy, and online mass-spectrometry to correlate the temperature, state of the catalyst and catalytic...... to self-reduction leading to extinction of the process. The latter was the key driver for the oscillations and thus gave additional insight into the mechanism of partial methane oxidation....

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)

Sensing in nature: using biomimetics for design of sensors

DEFF Research Database (Denmark)

Lenau, Torben Anker; Cheong, Hyunmin; Shu, Li

2010-01-01

The paper illustrates how biomimetics can be applied in sensor design. Biomimetics is an engineering discipline that uses nature as an inspiration source for generating ideas for how to solve engineering problems. Using biomimetics involves a search for relevant cases, a proper analysis...... of biomimetic studies of sense organs in animals....

Promotion Effect of CaO Modification on Mesoporous Al2O3-Supported Ni Catalysts for CO2 Methanation

Directory of Open Access Journals (Sweden)

Wen Yang

2016-01-01

Full Text Available The catalysts Ni/Al2O3 and CaO modified Ni/Al2O3 were prepared by impregnation method and applied for methanation of CO2. The catalysts were characterized by N2 adsorption/desorption, temperature-programmed reduction of H2 (H2-TPR, X-ray diffraction (XRD, and temperature-programmed desorption of CO2 and H2 (CO2-TPD and H2-TPD techniques, respectively. TPR and XRD results indicated that CaO can effectively restrain the growth of NiO nanoparticles, improve the dispersion of NiO, and weaken the interaction between NiO and Al2O3. CO2-TPD and H2-TPD results suggested that CaO can change the environment surrounding of CO2 and H2 adsorption and thus the reactants on the Ni atoms can be activated more easily. The modified Ni/Al2O3 showed better catalytic activity than pure Ni/Al2O3. Ni/CaO-Al2O3 showed high CO2 conversion especially at low temperatures compared to Ni/Al2O3, and the selectivity to CH4 was very close to 1. The high CO2 conversion over Ni/CaO-Al2O3 was mainly caused by the surface coverage by CO2-derived species on CaO-Al2O3 surface.

Surface tungsten reduction during thermal decomposition of ammonium paratungstate tetrahydrate in oxidising atmosphere: A paradox?

International Nuclear Information System (INIS)

Fait, Martin J.G.; Radnik, Jörg; Lunk, Hans-Joachim

2016-01-01

Highlights: • Detection of reduced tungsten ions at the solid’s surface in oxidising atmosphere. • Detection of gaseous ammonia liberated as oxidising agent. • Detection of ammonia’s oxidation products. • Quantification of the ammonia/tungsten redox process. - Abstract: The interaction of ammonia, liberated during thermal decomposition of ammonium paratungstate tetrahydrate in oxidising atmosphere, with tungsten has been studied employing a conventional microbalance combined with MS (Setaram’s instrument Sensys). Applying XPS a partial reduction of tungsten at the surface with the minimal tungsten oxidation number of +5.3 for a sample generated at 293 °C was detected. The balancing oxidation of ammonia to nitrogen/nitrogen oxides has been proven by MS. An amount of 0.049 mol e"− per mol W was transferred which resulted in an ammonia conversion degree from 2.1 mol% (NO_2 formation) to 3.0 mol% (N_2 formation).

Surface tungsten reduction during thermal decomposition of ammonium paratungstate tetrahydrate in oxidising atmosphere: A paradox?

Energy Technology Data Exchange (ETDEWEB)

Fait, Martin J.G., E-mail: martin.fait@catalysis.de [Leibniz-Institut für Katalyse e.V., Albert-Einstein-Strasse 29a, 18059 Rostock (Germany); Radnik, Jörg [Leibniz-Institut für Katalyse e.V., Albert-Einstein-Strasse 29a, 18059 Rostock (Germany); Lunk, Hans-Joachim [2858 Lake RD, Towanda, PA 18848 (United States)

2016-06-10

Highlights: • Detection of reduced tungsten ions at the solid’s surface in oxidising atmosphere. • Detection of gaseous ammonia liberated as oxidising agent. • Detection of ammonia’s oxidation products. • Quantification of the ammonia/tungsten redox process. - Abstract: The interaction of ammonia, liberated during thermal decomposition of ammonium paratungstate tetrahydrate in oxidising atmosphere, with tungsten has been studied employing a conventional microbalance combined with MS (Setaram’s instrument Sensys). Applying XPS a partial reduction of tungsten at the surface with the minimal tungsten oxidation number of +5.3 for a sample generated at 293 °C was detected. The balancing oxidation of ammonia to nitrogen/nitrogen oxides has been proven by MS. An amount of 0.049 mol e{sup −} per mol W was transferred which resulted in an ammonia conversion degree from 2.1 mol% (NO{sub 2} formation) to 3.0 mol% (N{sub 2} formation).

Bio-mimetic Flow Control

Science.gov (United States)

Choi, Haecheon

2009-11-01

Bio-mimetic engineering or bio-mimetics is the application of biological methods and systems found in nature to the study and design of engineering systems and modern technology (from Wikipedia). The concept itself is old, but successful developments have been made recently, especially in the research field of flow control. The objective of flow control based on the bio-mimetic approach is to develop novel concepts for reducing drag, increasing lift and enhancing aerodynamic performance. For skin friction reduction, a few ideas have been suggested such as the riblet from shark, compliant surface from dolphin, microbubble injection and multiple front-body curvature from penguin, and V-shaped protrusion from sailfish. For form drag reduction, several new attempts have been also made recently. Examples include the V-shaped spanwise grooves from saguaro cactus, overall shape of box fish, longitudinal grooves on scallop shell, bill of swordfish, hooked comb on owl wing, trailing-edge protrusion on dragonfly wing, and fillet. For the enhancement of aerodynamic performance, focuses have been made on the birds, fish and insects: e.g., double layered feather of landing bird, leading-edge serration of humpback-whale flipper, pectoral fin of flying fish, long tail on swallowtail-butterfly wing, wing flapping motion of dragonfly, and alula in birds. Living animals adapt their bodies to better performance in multi purposes, but engineering requires single purpose in most cases. Therefore, bio-mimetic approaches often produce excellent results more than expected. However, they are sometimes based on people's wrong understanding of nature and produce unwanted results. Successes and failures from bio-mimetic approaches in flow control will be discussed in the presentation.

CH{sub 4} reforming with CO{sub 2} for syngas production over nickel catalysts supported on mesoporous nanostructured γ-Al{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Majidian, Nasrollah; Habibi, Narges [Islamic Azad University, Tehran (Iran, Islamic Republic of); Rezaei, Mehran [University of Kashan, Kashan (Iran, Islamic Republic of)

2014-07-15

Nanostructured γ-Al{sub 2}O{sub 3} with high surface area and mesoporous structure was synthesized by sol-gel method and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by XRD, BET, TPR, TPH, SEM and TPO techniques. The BET analysis showed a high surface area of 204m{sup 2}g{sup -1} and a narrow pore-size distribution centered at a diameter of 5.5 nm for catalyst support. The results revealed that an increase in nickel loading from 5 to 15 wt% decreased the surface area of catalyst from 182 to 160 m{sup 2}g{sup -1}. In addition, the catalytic results showed an increase in methane conversion with increase in nickel content. TPO analysis revealed that the coke deposition increased with increasing in nickel loading, and the catalyst with 15 wt% of nickel showed the highest degree of carbon formation. SEM and TPH analyses confirmed the formation of whisker type carbon over the spent catalysts. Increasing CO{sub 2}/CH{sub 4} ratio increased the methane conversion. The BET analysis of spent catalysts indicated that the mesoporous structure of catalysts still remained after reaction.

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

Energy Technology Data Exchange (ETDEWEB)

Engelmann Pirez, M

2004-12-15

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

Methane synthesis under mild conditions for decentralized applications; Methansynthese unter milden Bedingungen fuer dezentrale Anwendungen

Energy Technology Data Exchange (ETDEWEB)

Schlueter, Michael [DBFZ Deutsches Biomasseforschungszentrum gGmbH, Leipzig (Germany); Roensch, Stefan

2016-08-01

It is a central aim of the German government to significantly reduce the emission of greenhouse gases in the next years. One possibility to reach this aim is the substitution of fossil fuels, especially natural gas, by fuels from biogenic sources (Bio-SNG). However, it is a drawback of Bio-SNG that the production costs are considerably higher than those of fossil natural gas. This work provides an approach to reduce the production costs of Bio-SNG. It is the aim to reduce the process parameters of the methane synthesis. At the same time, it has to be ensured that high methane yields are achieved even at those mild conditions. A procedure for the optimization of the methanation catalyst activity will be presented. If the catalyst is as active as possible even at mild conditions, it will be possible to produce Bio-SNG cost efficient even in small, decentralized scale.

Production of cellulose and hemicellulose-degrading enzymes by filamentous fungi cultivated on wet-oxidised wheat straw

DEFF Research Database (Denmark)

Thygesen, A.; Thomsen, A.B.; Schmidt, A.S.

2003-01-01

The production of cellulose and hemicellulose-degrading enzymes by cultivation of Aspergillus niger ATCC 9029, Botrytis cinerea ATCC 28466, Penicillium brasilianum IBT 20888, Schizophyllum commune ATCC 38548, and Trichoderma reesei Rut-C30 was studied. Wet-oxidised wheat straw suspension suppleme......The production of cellulose and hemicellulose-degrading enzymes by cultivation of Aspergillus niger ATCC 9029, Botrytis cinerea ATCC 28466, Penicillium brasilianum IBT 20888, Schizophyllum commune ATCC 38548, and Trichoderma reesei Rut-C30 was studied. Wet-oxidised wheat straw suspension...... hydrolysis of filter cake from wet-oxidised wheat straw for 48 h with an enzyme loading of 5 FPU/g biomass resulted in glucose yields from cellulose of 58% (w/w) and 39% (w/w) using enzymes produced by R brasilianum and a commercial enzyme mixture, respectively. At higher enzyme loading (25 FPU/g biomass...

Biomimetics

Indian Academy of Sciences (India)

M. Senthilkumar (Newgen Imaging) 1461 1996 Oct 15 13:05:22

Abstract. The well-organised multifunctional structures, systems and biogenic materials found in nature have attracted the interest of scientists working in many disciplines. The efforts have resulted in the development of a new and rapidly growing field of scientific effort called biomimetics. In this article we present a.

Catalytic removal of methane and NO{sub x} in lean-burn natural-gas engine exhaust; Elimination par catalyse du methane et des NO{sub x} dans les echappements de moteur au gaz naturel a basse combustion

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, H.; Satokawa, S.; Yahagi, M.; Yamaseki, K.; Hoshi, F.; Uchida, H.; Yokota, H. [Tokyo Gas Co., Ltd. (Japan)

2000-07-01

We have developed a new catalytic system to reduce the emissions of hydrocarbons, carbon monoxide (CO), and nitrogen oxides (NO{sub x}) contained in the exhaust gases from a lean-burn natural-gas engine. Catalytic oxidation of unburned hydrocarbons and CO in the exhaust has been studied for noble metals supported on alumina. (1) A low-loading catalyst comprising platinum supported on alumina (Pt/alumina) was efficient for the oxidation of CO and hydrocarbons without methane. The CO conversions were maintained at more than 98 % for 20,000 hours over the Pt/alumina. (2) A catalyst comprising platinum and palladium supported on alumina (Pt-Pd/alumina) exhibited higher levels of oxidation of hydrocarbons (including methane) than a catalyst comprising only palladium supported on alumina (Pd/alumina). Its oxidation also lasted longer. The combined effects of the platinum and palladium metals achieved high sulfur dioxide resistance. Increasing the palladium content in the Pt-Pd/alumina catalyst increased the level of oxidation and extended the lifetime of the catalyst. (3) A catalyst comprising silver supported on alumina (Ag/alumina) was effective at reducing the amount of NO{sub X} by using the unburned hydrocarbons in the exhaust gas. The NO{sub x} conversions over Ag/alumina were maintained at more than 30 % for 3,500 hours. We describe a total clean-up system consisting of a Ag/alumina catalyst and a Pt-Pd/alumina catalyst in series on the exhaust gas stream. (authors)

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

Science.gov (United States)

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

2017-08-02

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

Rh promoted La{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 3-δ} perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

Energy Technology Data Exchange (ETDEWEB)

Palcheva, R., E-mail: radost@ic.bas.bg [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway); Olsbye, U.; Palcut, M. [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway); Rauwel, P. [Department of Physics, SMN, University of Oslo, PO Box B 1048 Blindern, Oslo 0316 (Norway); Tyuliev, G.; Velinov, N. [Institute of Catalysis, Bulgarian Academy of Sciences, G. Bonchev Str., Bldg. 11, Sofia 1113 (Bulgaria); Fjellvåg, H.H. [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway)

2015-12-01

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

BIOMIMETIC STRATEGIES IN ORGANIC SYNTHESIS. TERPENES

Directory of Open Access Journals (Sweden)

V. Kulcitki

2012-12-01

Full Text Available The current paper represents an outline of the selected contributions to the biomimetic procedures and approaches for the synthesis of terpenes with complex structure and diverse functionalisation pattern. These include homologation strategies, cyclisations, rearrangements, as well as biomimetic remote functionalisations.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

Science.gov (United States)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

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.

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.

Evolving application of biomimetic nanostructured hydroxyapatite

Directory of Open Access Journals (Sweden)

Norberto Roveri

2010-11-01

Full Text Available Norberto Roveri, Michele IafiscoLaboratory of Environmental and Biological Structural Chemistry (LEBSC, Dipartimento di Chimica ‘G. Ciamician’, Alma Mater Studiorum, Università di Bologna, Bologna, ItalyAbstract: By mimicking Nature, we can design and synthesize inorganic smart materials that are reactive to biological tissues. These smart materials can be utilized to design innovative third-generation biomaterials, which are able to not only optimize their interaction with biological tissues and environment, but also mimic biogenic materials in their functionalities. The biomedical applications involve increasing the biomimetic levels from chemical composition, structural organization, morphology, mechanical behavior, nanostructure, and bulk and surface chemical–physical properties until the surface becomes bioreactive and stimulates cellular materials. The chemical–physical characteristics of biogenic hydroxyapatites from bone and tooth have been described, in order to point out the elective sides, which are important to reproduce the design of a new biomimetic synthetic hydroxyapatite. This review outlines the evolving applications of biomimetic synthetic calcium phosphates, details the main characteristics of bone and tooth, where the calcium phosphates are present, and discusses the chemical–physical characteristics of biomimetic calcium phosphates, methods of synthesizing them, and some of their biomedical applications.Keywords: hydroxyapatite, nanocrystals, biomimetism, biomaterials, drug delivery, remineralization

'Methane oxidation on supported gold catalysts'

DEFF Research Database (Denmark)

Walther, Guido

2008-01-01

steady-state activity measurements were performed to obtain the reaction rates for CO and H2 oxidation. These reactions were studied on three different gold particle sizes using either O2 or N2O as oxidation agents. Using particle size distributions obtained from TEM analysis, it was found that the CO......Methane (CH4), a major compound of natural gas, has been suggested as a future energy carrier. However, it is also known to be a strong greenhouse gas. The use of CH4 obtained from crude oil as an associated gas is often uneconomical, and it is thus burned off. Avoiding flaring and making...... the energy stored in the molecule available, is a major research challenge. In this PhD thesis, CH4 oxidation on nanoparticular gold is studied both experimentally and theoretically. In the course of this PhD project, CH4 oxidation was experimentally found more likely to form CO2 and H2O than other low index...

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

Directory of Open Access Journals (Sweden)

Silvia Sálua Maluf

2003-03-01

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

Low-temperature upgrading of low-calorific biogas for CO2 mitigation using DBD-catalyst hybrid reactor

Science.gov (United States)

Nozaki, Tomohiro; Tsukijihara, Hiroyuki; Fukui, Wataru; Okazaki, Ken

2006-10-01

Although huge amounts of biogas, which consists of 20-60% of CH4 in CO2/N2, can be obtained from landfills, coal mines, and agricultural residues, most of them are simply flared and wasted: because global warming potential of biogas is 5-15 times as potent as CO2. Poor combustibility of such biogas makes it difficult to utilize in conventional energy system. The purpose of this project is to promote the profitable recovery of methane from poor biogas via non-thermal plasma technology. We propose low-temperature steam reforming of biogas using DBD generated in catalyst beds. Methane is partially converted into hydrogen, and then fed into internal combustion engines for improved ignition stability as well as efficient operation. Low-temperature steam reforming is beneficial because exhaust gas from an engine can be used to activate catalyst beds. Space velocity (3600-15000 hr-1), reaction temperature (300-650^oC), and energy cost (30-150 kJ per mol CH4) have been investigated with simulated biogas (20-60% CH4 in mixtures of CO2/N2). The DBD enhances reaction rate of CH4 by a factor of ten at given catalyst temperatures, which is a rate-determining step of methane steam reforming, while species concentration of upgraded biogas was governed by thermodynamic equilibrium in the presence of catalyst.

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

Energy Technology Data Exchange (ETDEWEB)

Engelmann Pirez, M

2004-12-15

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

Total knee arthroplasty with an oxidised zirconium femoral component: ten-year survivorship analysis.

Science.gov (United States)

Ahmed, I; Salmon, L J; Waller, A; Watanabe, H; Roe, J P; Pinczewski, L A

2016-01-01

Oxidised zirconium was introduced as a material for femoral components in total knee arthroplasty (TKA) as an attempt to reduce polyethylene wear. However, the long-term survival of this component is not known. We performed a retrospective review of a prospectively collected database to assess the ten year survival and clinical and radiological outcomes of an oxidised zirconium total knee arthroplasty with the Genesis II prosthesis. The Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC), Knee Injury and Osteoarthritis Outcome Score (KOOS) and a patient satisfaction scale were used to assess outcome. A total of 303 consecutive TKAs were performed in 278 patients with a mean age of 68 years (45 to 89). The rate of survival ten years post-operatively as assessed using Kaplan-Meier analysis was 97% (95% confidence interval 94 to 99) with revision for any reason as the endpoint. There were no revisions for loosening, osteolysis or failure of the implant. There was a significant improvement in all components of the WOMAC score at final follow-up (p zirconium TKA gives comparable rates of survival with other implants and excellent functional outcomes ten years post-operatively. Total knee arthroplasty with an oxidised zirconium femoral component gives comparable long-term rates of survival and functional outcomes with conventional implants. ©2016 The British Editorial Society of Bone & Joint Surgery.

Biomimetics: forecasting the future of science, engineering, and medicine.

Science.gov (United States)

Hwang, Jangsun; Jeong, Yoon; Park, Jeong Min; Lee, Kwan Hong; Hong, Jong Wook; Choi, Jonghoon

2015-01-01

Biomimetics is the study of nature and natural phenomena to understand the principles of underlying mechanisms, to obtain ideas from nature, and to apply concepts that may benefit science, engineering, and medicine. Examples of biomimetic studies include fluid-drag reduction swimsuits inspired by the structure of shark's skin, velcro fasteners modeled on burrs, shape of airplanes developed from the look of birds, and stable building structures copied from the backbone of turban shells. In this article, we focus on the current research topics in biomimetics and discuss the potential of biomimetics in science, engineering, and medicine. Our report proposes to become a blueprint for accomplishments that can stem from biomimetics in the next 5 years as well as providing insight into their unseen limitations.

Biomimetics: forecasting the future of science, engineering, and medicine

Science.gov (United States)

Hwang, Jangsun; Jeong, Yoon; Park, Jeong Min; Lee, Kwan Hong; Hong, Jong Wook; Choi, Jonghoon

2015-01-01

Biomimetics is the study of nature and natural phenomena to understand the principles of underlying mechanisms, to obtain ideas from nature, and to apply concepts that may benefit science, engineering, and medicine. Examples of biomimetic studies include fluid-drag reduction swimsuits inspired by the structure of shark’s skin, velcro fasteners modeled on burrs, shape of airplanes developed from the look of birds, and stable building structures copied from the backbone of turban shells. In this article, we focus on the current research topics in biomimetics and discuss the potential of biomimetics in science, engineering, and medicine. Our report proposes to become a blueprint for accomplishments that can stem from biomimetics in the next 5 years as well as providing insight into their unseen limitations. PMID:26388692

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

The improved stability of enzyme encapsulated in biomimetic titania particles

International Nuclear Information System (INIS)

Jiang Yanjun; Sun Qianyun; Jiang Zhongyi; Zhang Lei; Li Jian; Li Lin; Sun Xiaohui

2009-01-01

This study demonstrates a novel biomimetic approach for the entrapment of yeast alcohol dehydrogenase (YADH) within titania nanoparticles to improve its stability. Protamine was as the template and catalyst for the condensation of titanium (IV) bis(ammonium lactato) dihydroxide (Ti-BALDH) into titania nanoparticles in which YADH was trapped. The as-prepared titania/protamine/YADH composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The mechanism of YADH encapsulation was tentatively proposed from a series of experimental results. The preliminary investigation showed that encapsulated YADH could retain most of its initial activity. Compared to free YADH, encapsulated YADH exhibited significantly improved thermal, pH and recycling stability. After 5 weeks storage, no substantial loss of catalytic activity for encapsulated YADH was observed

Photosynthesis of hydrogen and methane as key components for clean energy system

Directory of Open Access Journals (Sweden)

Seng Sing Tan et al

2007-01-01

Full Text Available While researchers are trying to solve the world's energy woes, hydrogen is becoming the key component in sustainable energy systems. Hydrogen could be produced through photocatalytic water-splitting technology. It has also been found that hydrogen and methane could be produced through photocatalytic reduction of carbon dioxide with water. In this exploratory study, instead of coating catalysts on a substrate, pellet form of catalyst, which has better adsorption capacity, was used in the photo-reduction of carbon dioxide with water. In the experiment, some water was first absorbed into titanium dioxide pellets. Highly purified carbon dioxide gas was then discharged into a reactor containing these wet pellets, which were then illuminated continuously using UVC lamps. Gaseous samples accumulated in the reactor were extracted at different intervals to analyze the product yields. The results confirmed that methane and hydrogen were photosynthesized using pellet form of TiO2 catalysts. Hydrogen was formed at a rate as high as 0.16 micromoles per hour (μmol h−1. The maximum formation rate of CH4 was achieved at 0.25 μmol h−1 after 24 h of irradiation. CO was also detected.

Effects of oxidised oil and vitamin E on performance and some blood ...

African Journals Online (AJOL)

hakan

oxidised dietary oil nor vitamin E supplementation had any adverse effect on weight ..... group (0.60 ± 0.05 µM) might be a sign of the beneficial effect of vitamin E in alleviating oxidative damage .... of single oxygen and radicals (Surai, 2003).

Catalytic Methane Decomposition over Fe-Al2O3

KAUST Repository

Zhou, Lu; Enakonda, Linga Reddy; Saih, Youssef; Loptain, Sergei; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

2016-01-01

The presence of a Fe-FeAl2O4 structure over an Fe-Al2O3 catalysts is demonstrated to be vital for the catalytic methane decomposition (CMD) activity. After H2 reduction at 750°C, Fe-Al2O3 prepared by means of a fusion method, containing 86.5wt% Fe

Biomimetics applied to centering in micro-assembly

DEFF Research Database (Denmark)

Shu, L.H.; Lenau, Torben Anker; Hansen, Hans Nørgaard

2003-01-01

This paper describes the application of a biomimetic search method to develop ideas for centering objects in micro-assembly. Biomimetics involves the imitation of biological phenomena to solve problems. An obstacle to the use of biomimetics in engineering is knowledge of biological phenomena...... that is relevant to the problem at hand. The method described here starts with an engineering problem, and then systematically searches for analogous biological phenomena using functional keywords. This method is illustrated by finding and using analogies for the problem of positioning and centering objects during...

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.

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.

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.

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.

Catalytic combustion of methane over mixed oxides derived from Co-Mg/Al ternary hydrotalcites

Energy Technology Data Exchange (ETDEWEB)

Jiang, Zheng [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Research Centre of Eco-Environmental Sciences, CAS, Beijing 100085 (China); Jesus College, University of Oxford, OX1 3DW (United Kingdom); Yu, Junjie; Cheng, Jie; Hao, Zhengping [Research Centre of Eco-Environmental Sciences, CAS, Beijing 100085 (China); Xiao, Tiancun; Edwards, Peter P. [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Jones, Martin O. [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Rutherford Appleton Laboratory, Didcot, OX11 0QX (United Kingdom)

2010-01-15

Co{sub x}Mg{sub 3-x} /Al composite oxides (xCoMAO-800) were prepared by calcination of Co{sub x}Mg{sub 3-x}/Al hydrotalcites (x=0.0,0.5,1.0,1.5,2.0,2.5,3.0, respectively) at 800 C. The materials were characterized using XRD, TG-DSC, N{sub 2} adsorption-desorption and TPR. The methane catalytic combustion over the xCoMAO-800 was assessed in a fixed bed micro-reactor. The results revealed that cobalt can be homogenously dispersed into the matrices of the hydrotalcites and determines the structure, specific surface areas and porosity of the derived xCoMAO-800 oxide catalysts. The thermal stability and homogeneity of the hydrotalcites markedly depends on the cobalt concentration in the hydrotalcites. The Co-based hydrotalcite-derived oxides exhibit good activity in the catalytic combustion of methane. The catalytic activity over the xCoMAO-800 oxides enhances with increasing x up to 1.5, but subsequently decreases dramatically as cobalt loadings are further increased. The 1.5CoMAO-800 catalyst shows the best methane combustion activity, igniting methane at 450 C and completing methane combustion around 600 C. The catalytic combustion activity over the xCoMAO-800 oxides are closely related to the strong Co-Mg/Al interaction within the mixed oxides according to the TG-DSC, TPR and activity characteristics. (author)

[Towards computer-aided catalyst design: Three effective core potential studies of C-H activation]. Final report

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-12-31

Research in the initial grant period focused on computational studies relevant to the selective activation of methane, the prime component of natural gas. Reaction coordinates for methane activation by experimental models were delineated, as well as the bonding and structure of complexes that effect this important reaction. This research, highlighted in the following sections, also provided the impetus for further development, and application of methods for modeling metal-containing catalysts. Sections of the report describe the following: methane activation by multiple-bonded transition metal complexes; computational lanthanide chemistry; and methane activation by non-imido, multiple-bonded ligands.

Biomimetic design method for innovation and sustainability

CERN Document Server

Helfman Cohen, Yael

2017-01-01

Presenting a novel biomimetic design method for transferring design solutions from nature to technology, this book focuses on structure-function patterns in nature and advanced modeling tools derived from TRIZ, the theory of inventive problem-solving. The book includes an extensive literature review on biomimicry as an engine of both innovation and sustainability, and discusses in detail the biomimetic design process, current biomimetic design methods and tools. The structural biomimetic design method for innovation and sustainability put forward in this text encompasses (1) the research method and rationale used to develop and validate this new design method; (2) the suggested design algorithm and tools including the Findstructure database, structure-function patterns and ideality patterns; and (3) analyses of four case studies describing how to use the proposed method. This book offers an essential resource for designers who wish to use nature as a source of inspiration and knowledge, innovators and sustain...

Legionella control in power station cooling towers using oxidising biocides

Energy Technology Data Exchange (ETDEWEB)

Sailer, Christian; Rawlinson, Julia; Killeen, Paul [Ecolab PTY LTD, Ascot, WA (Australia)

2009-02-15

Power stations have used oxidising biocides such as chlorine or bromine for many years to control microbial growth in their cooling towers. In this paper Ecolab trademark looks at the direct effect halogen concentration has on Legionella populations in order to determine the most effective halogenation rate required to ensure that the site key performance indicator (KPI) of < 100 colony-forming units (cfu) per mL can be maintained. (orig.)

Biomimetic membranes for sensor and separation applications

CERN Document Server

2012-01-01

This book addresses the possibilities and challenges in mimicking biological membranes and creating membrane-based sensor and separation devices. It covers recent advances in developing biomimetic membranes for technological applications with a focus on the use of integral membrane protein mediated transport. It describes the fundamentals of biosensing as well as separation and shows how the two processes work together in biological systems. The book provides an overview of the current state of the art, points to areas that need further investigation and anticipates future directions in the field. Biomimetics is a truly cross-disciplinary approach and this is exemplified by the challenges in mimicking osmotic processes as they occur in nature using aquaporin protein water channels as central building blocks. In the development of a biomimetic sensor/separation technology, both channel and carrier proteins are important and examples of how these may be reconstituted and controlled in biomimetic membranes are ...

Synthesis and characterization of PtRu/C catalysts obtained by colloidal and deposition methods for fuel cell applications

Directory of Open Access Journals (Sweden)

Egberto Gomes Franco

2005-06-01

Full Text Available The purpose of this investigation was to compare catalysts produced by the Bönnemann - colloidal method (PtRu (B1 and PtRu (B2, and those produced by the spontaneous deposition method (PtRu (SD. The catalysts produced by both methods had good electrochemical behavior for methanol oxidation for proton exchange membrane fuel cell applications. The structure of the catalyst was examined by transmission electron microscopy (TEM. Energy dispersive spectroscopic analysis (EDS was used to determine the semi-quantitative composition of the catalysts, and the electrochemical behavior was determined by cyclic voltammetry (CV. The diffractograms of the binary catalysts revealed platinum and ruthenium as the only crystalline phases, as per ICDD data base. The PtRu (B1 catalyst, treated in a reducing atmosphere, has the same structure as PtRu (B2, treated in an oxidising/reducing atmosphere, except that the crystallite size was around 1.7 nm for PtRu (B1 instead of 9.9 nm for PtRu (B2. The catalysts PtRu (B2 and PtRu (SD showed similar cyclic voltammetric behavior, which was better than that of PtRu (B1. Both methods are suitable for the production of electrocatalysts for fuel cell applications. The colloidal method is more expensive than the deposition method, but the former permits the production of ternary and quaternary catalyst systems with enhanced CO tolerance.

FiveS rRNA sequences and fatty acid profiles of colourless sulfur-oxidising bacteria

Digital Repository Service at National Institute of Oceanography (India)

LokaBharathi, P.A.; Ortiz-conde, B.A.; Nair, S.; Chandramohan, D.; Colwell, R.R.

Colourless sulfur-oxidising bacteria have been encountered extensively in the oxygen minimum layers of the Arabian Sea. These oligotrophs have been known to mediate nitrogen cycle reductively even under autotrophic conditions. Some...

Biomimetic Materials and Fabrication Approaches for Bone Tissue Engineering.

Science.gov (United States)

Kim, Hwan D; Amirthalingam, Sivashanmugam; Kim, Seunghyun L; Lee, Seunghun S; Rangasamy, Jayakumar; Hwang, Nathaniel S

2017-12-01

Various strategies have been explored to overcome critically sized bone defects via bone tissue engineering approaches that incorporate biomimetic scaffolds. Biomimetic scaffolds may provide a novel platform for phenotypically stable tissue formation and stem cell differentiation. In recent years, osteoinductive and inorganic biomimetic scaffold materials have been optimized to offer an osteo-friendly microenvironment for the osteogenic commitment of stem cells. Furthermore, scaffold structures with a microarchitecture design similar to native bone tissue are necessary for successful bone tissue regeneration. For this reason, various methods for fabricating 3D porous structures have been developed. Innovative techniques, such as 3D printing methods, are currently being utilized for optimal host stem cell infiltration, vascularization, nutrient transfer, and stem cell differentiation. In this progress report, biomimetic materials and fabrication approaches that are currently being utilized for biomimetic scaffold design are reviewed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Effects of Mn- and K-addition on catalytic activity of calcium oxide for methane activation

International Nuclear Information System (INIS)

Park, Jong Sik; Kong, Jang Il; Lee, Sung Han; Jun, Jong Ho

1998-01-01

Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800 .deg. C to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction (XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally p(CH 4 )/p(O 2 )=250 Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best C 2 yield of 8.0% with a selectivity of 43.2% at 775 .deg. C. The C 2 selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO((Mn)>6.3 mol%)catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the C 2 selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000 .deg. C at Po2's of 10 -3 to 10 -1 atm. The electrical conductivity was decreased with Mn-doping and increased with increasing Po 2 in the range of 10 -3 to 10 -1 atm, indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry

Cyclic process for producing methane from carbon monoxide with heat removal

Science.gov (United States)

Frost, Albert C.; Yang, Chang-lee

1982-01-01

Carbon monoxide-containing gas streams are converted to methane by a cyclic, essentially two-step process in which said carbon monoxide is disproportionated to form carbon dioxide and active surface carbon deposited on the surface of a catalyst, and said carbon is reacted with steam to form product methane and by-product carbon dioxide. The exothermic heat of reaction generated in each step is effectively removed during each complete cycle so as to avoid a build up of heat from cycle-to-cycle, with particularly advantageous techniques being employed for fixed bed, tubular and fluidized bed reactor operations.

Hydrogen--deuterium exchange in saturated hydrocarbons on α-chromia catalyst

International Nuclear Information System (INIS)

Kalman, J.; Guczi, L.

1977-01-01

The kinetics of hydrogen--deuterium exchange in methane, ethane, and propane have been studied with unsupported α-chromia as catalyst in the temperature range of 598 to 688 0 K. The apparent activation energies for methane, ethane, and propane are 88, 130, and 84 kJ mol -1 , respectively, similar to those found on chromia gel. The order of reaction with respect to hydrocarbons and deuterium has been determined as also having the kinetic isotope effect. The main initial products are CH 3 D and CD 4 with methane, C 2 H 4 D 2 and C 2 D 6 with ethane, and C 3 H 7 D and C 3 D 8 with propane. A change in product distribution as a function of temperature, conversion, aging, and oxygen--deuterium treatment has been observed. In agreement with the kinetic data and the effect of oxygen, Cr 3+ has been assumed as the active species of the chromia catalyst, whereas Cr 2+ is an inactive site on the surface. There is no direct proof that chromium ion in a valence state higher than 3+ plays an important role in the exchange reaction. It was established that dual Cr 3+ -- Cr 3+ sites are responsible for the formation of ethane-d 2 . After a long deuterium treatment the number of dual sites is decreased, the effect being revealed in the decreased rate of exchange and the small amount of ethane-d 2 . On the contrary, the formation of methane-d 4 is interpreted by the formation of Cr = C bonds by analogy with homogeneous complexes. In the case of propane, the exchange reaction can be adequately interpreted by a π-allyl mechanism

Selective coke combustion by oxygen pulsing during Mo/ZSM‐5‐catalyzed methane dehydroaromatization

NARCIS (Netherlands)

Kosinov, N.; Coumans, F.J.A.G.; Uslamin, E.A.; Kapteijn, F.; Hensen, E.J.M.

2016-01-01

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

Biomimetic High-Density Lipoproteins from a Gold Nanoparticle Template

Science.gov (United States)

Luthi, Andrea Jane

For hundreds of years the field of chemistry has looked to nature for inspiration and insight to develop novel solutions for the treatment of human diseases. The ability of chemists to identify, mimic, and modifiy small molecules found in nature has led to the discovery and development of many important therapeutics. Chemistry on the nanoscale has made it possible to mimic natural, macromolecular structures that may also be useful for understanding and treating diseases. One example of such a structure is high-density lipoprotein (HDL). The goal of this work is to use a gold nanoparticle (Au NP) as a template to synthesize functional mimics of HDL and characterize their structure and function. Chapter 1 details the structure and function of natural HDL and how chemistry on the nanoscale provides new strategies for mimicking HDL. This Chapter also describes the first examples of using nanoparticles to mimic HDL. Chapter 2 reports the synthesis and characterization of biomimetic HDL using different sizes of Au NPs and different surface chemistries and how these variables can be used to tailor the properties of biomimetic HDL. From these studies the optimal strategy for synthesizing biomimetic HDL was determined. In Chapter 3, the optimization of the synthesis of biomimetic HDL is discussed as well as a full characterization of its structure. In addition, the work in this chapter shows that biomimetic HDL can be synthesized on a large scale without alterations to its structure or function. Chapter 4 focuses on understanding the pathways by which biomimetic HDL accepts cholesterol from macrophage cells. The results of these studies demonstrate that biomimetic HDL is able to accept cholesterol by both active and passive pathways of cholesterol efflux. In Chapter 5 the preliminary results of in vivo studies to characterize the pharmacokinetics and pharmacodynamics of biomimetic HDL are presented. These studies suggest that biomimetic HDL traffics through tissues prone to

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)

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.

Assessment of the methane oxidation capacity of compacted soils intended for use as landfill cover materials

International Nuclear Information System (INIS)

Rachor, Ingke; Gebert, Julia; Groengroeft, Alexander; Pfeiffer, Eva-Maria

2011-01-01

The microbial oxidation of methane in engineered cover soils is considered a potent option for the mitigation of emissions from old landfills or sites containing wastes of low methane generation rates. A laboratory column study was conducted in order to derive design criteria that enable construction of an effective methane oxidising cover from the range of soils that are available to the landfill operator. Therefore, the methane oxidation capacity of different soils was assessed under simulated landfill conditions. Five sandy potential landfill top cover materials with varying contents of silt and clay were investigated with respect to methane oxidation and corresponding soil gas composition over a period of four months. The soils were compacted to 95% of their specific proctor density, resulting in bulk densities of 1.4-1.7 g cm -3 , reflecting considerably unfavourable conditions for methane oxidation due to reduced air-filled porosity. The soil water content was adjusted to field capacity, resulting in water contents ranging from 16.2 to 48.5 vol.%. The investigated inlet fluxes ranged from 25 to about 100 g CH 4 m -2 d -1 , covering the methane load proposed to allow for complete oxidation in landfill covers under Western European climate conditions and hence being suggested as a criterion for release from aftercare. The vertical distribution of gas concentrations, methane flux balances as well as stable carbon isotope studies allowed for clear process identifications. Higher inlet fluxes led to a reduction of the aerated zone, an increase in the absolute methane oxidation rate and a decline of the relative proportion of oxidized methane. For each material, a specific maximum oxidation rate was determined, which varied between 20 and 95 g CH 4 m -2 d -1 and which was positively correlated to the air-filled porosity of the soil. Methane oxidation efficiencies and gas profile data imply a strong link between oxidation capacity and diffusive ingress of

Reverse Engineering Nature to Design Biomimetic Total Knee Implants.

Science.gov (United States)

Varadarajan, Kartik Mangudi; Zumbrunn, Thomas; Rubash, Harry E; Malchau, Henrik; Muratoglu, Orhun K; Li, Guoan

2015-10-01

While contemporary total knee arthroplasty (TKA) provides tremendous clinical benefits, the normal feel and function of the knee is not fully restored. To address this, a novel design process was developed to reverse engineer "biomimetic" articular surfaces that are compatible with normal soft-tissue envelope and kinematics of the knee. The biomimetic articular surface is created by moving the TKA femoral component along in vivo kinematics of normal knees and carving out the tibial articular surface from a rectangular tibial block. Here, we describe the biomimetic design process. In addition, we utilize geometric comparisons and kinematic simulations to show that; (1) tibial articular surfaces of conventional implants are fundamentally incompatible with normal knee motion, and (2) the anatomic geometry of the biomimetic surface contributes directly to restoration of normal knee kinematics. Such biomimetic implants may enable us to achieve the long sought after goal of a "normal" knee post-TKA surgery. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

Pore-Confined Carriers and Biomolecules in Mesoporous Silica for Biomimetic Separation and Targeting

Science.gov (United States)

Zhou, Shanshan

Selectively permeable biological membranes composed of lipophilic barriers inspire the design of biomimetic carrier-mediated membranes for aqueous solute separation. This work imparts selective permeability to lipid-filled pores of silica thin film composite membranes using carrier molecules that reside in the lipophilic self-assemblies. The lipids confined inside the pores of silica are proven to be a more effective barrier than bilayers formed on the porous surface through vesicle fusion, which is critical for quantifying the function of an immobilized carrier. The ability of a lipophilic carrier embedded in the lipid bilayer to reversibly bind the target solute and transport it through the membrane is demonstrated. Through the functionalization of the silica surface with enzymes, enzymatic catalysis and biomimetic separations can be combined on this nanostructured composite platform. The successful development of biomimetic nanocomposite membrane can provide for efficient dilute aqueous solute upgrading or separations using engineered carrier/catalyst/support systems. While the carrier-mediated biomimetic membranes hold great potential, fully understanding of the transport processes in composite synthetic membranes is essential for improve the membrane performance. Electrochemical impedance spectroscopy (EIS) technique is demonstrated to be a useful tool for characterizing the thin film pore accessibility. Furthermore, the effect of lipid bilayer preparation methods on the silica thin film (in the form of pore enveloping, pore filling) on ion transport is explored, as a lipid bilayer with high electrically insulation is essential for detecting activity of proteins or biomimetic carriers in the bilayer. This study provides insights for making better barriers on mesoporous support for carrier-mediated membrane separation process. Porous silica nanoparticles (pSNPs) with pore sizes appropriate for biomolecule loading are potential for encapsulating dsRNA within the

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.

Evaluation of a fuel cell polymer electrolyte with Pt-Sn anode operating with H2, H2-CO mixture, propane and methane

International Nuclear Information System (INIS)

Monsalve, Carlos; Hoyos, Bibian

2005-01-01

In this work it was tested a proton Exchange membrane fuel cell with a Pt-Sn anode (in a 90:10 ratio) fed with H 2 , a H 2 -CO mixture, propane and methane under a pressure of 10 psi and temperatures of 30, 50 y 70 Celsius degrade. It was found good catalyst tolerance to the CO presence in the hydrogen current, even with catalytic activity to the CO oxidation. For the pure CO, propane and methane cases, the catalytic activity was too low. This results show that the Pt-Sn catalyst it is not appropriated for those fuels.

Biomimetic mineral coatings in dental and orthopaedic implantology

NARCIS (Netherlands)

Liu, Y.; de Groot, K.; Hunziker, E.B.

2009-01-01

Biomimetic techniques are used to deposit coatings of calcium phosphate upon medical devices. The procedure is conducted under near-physiological, or "biomimetic", conditions of temperature and pH primarily to improve their biocompatibility and biodegradability of the materials. The inorganic layers

Methane Emissions from Landfill: Isotopic Evidence for Low Percentage of Oxidation from Gas Wells, Active and Closed Cells

Science.gov (United States)

Lowry, David; Fisher, Rebecca; Zazzeri, Giulia; al-Shalaan, Aalia; France, James; Lanoisellé, Mathias; Nisbet, Euan

2017-04-01

Large landfill sites remain a significant source of methane emissions in developed and developing countries, with a global estimated flux of 29 Tg / yr in the EDGAR 2008 database. This is significantly lower than 20 years ago due to the introduction of gas extraction systems, but active cells still emit significant amounts of methane before the gas is ready for extraction. Historically the methane was either passively oxidized through topsoil layers or flared. Oxidation is still the primary method of methane removal in many countries, and covered, remediated cells across the world continue to emit small quantities of methane. The isotopic signatures of methane from landfill gas wells, and that emitted from active and closed cells have been characterized for more than 20 UK landfills since 2011, with more recent work in Kuwait and Hong Kong. Since 2013 the emission plumes have been identified by a mobile measurement system (Zazzeri et al., 2015). Emissions in all 3 countries have a characteristic δ13C signature of -58 ± 3 ‰ dominated by emissions from the active cells, despite the hot, dry conditions of Kuwait and the hot, humid conditions of Hong Kong. Gas well samples define a similar range. Surface emissions from closed cells and closed landfills are mostly in the range -56 to -52 ‰Ṫhese are much more depleted values than those observed in the 1990s (up to -35 ) when soil oxidation was the dominant mechanism of methane removal. Calculations using isotopic signatures of the amount of methane oxidised in these closed areas before emission to atmosphere range from 5 to 15%, but average less than 10%, and are too small to calculate from the high-emitting active cells. Compared to other major methane sources, landfills have the most consistent isotopic signature globally, and are distinct from the more 13C-enriched natural gas, combustion and biomass burning sources. Zazzeri, G. et al. (2015) Plume mapping and isotopic characterization of anthropogenic methane

Biomimetic superwettable materials with structural colours.

Science.gov (United States)

Wang, Zelinlan; Guo, Zhiguang

2017-12-05

Structural colours and superwettability are of great interest due to their unique characteristics. However, the application of materials with either structural colours or superwettability is limited. Moreover, materials possessing both structural colours and superwettability are crucial for many practical applications. The combination of structural colours and superwettability can result in materials for use various applications, such as in sensors, detectors, bioassays, anti-counterfeiting, and liquid actuators, by controlling surfaces to repel or absorb liquids. Regarding superwettability and structural colours, surface texture and chemical composition are two factors for the construction of materials with superwettable structural colours. This review aims at offering a comprehensive elaboration of the mechanism, recent biomimetic research, and applications of biomimetic superwettable materials with structural colours. Furthermore, this review provides significant insight into the design, fabrication, and application of biomimetic superwettable materials with structural colours.

Challenges in biomimetic design and innovation

DEFF Research Database (Denmark)

Lenau, Torben Anker; Barfoed, Michael; Shu, Li

Biomimetic design copies desired principles found in nature and implement them into artificial applications. Applications could be products we use in our daily life but it can also be used to inspire material innovation. However there are significant challenges in performing biomimetic design. One....... This is a key issue in design and innovation work where problem identification and systematic search for suitable solution principle are major activities. One way to deal with this challenge is to use a biology search method. The use of such a method is illustrated with a case story describing the design...... including the terminology and knowledge organisation. It is often easy to recognise the splendour of a biological solution, but it can be much more difficult to understand the underlying mechanisms. Another challenge in biomimetic design is the search and identification of relevant solutions in nature...

Sabatier Catalyst Poisoning Investigation

Science.gov (United States)

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

2013-01-01

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

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...

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.

Genome-Guided Analysis and Whole Transcriptome Profiling of the Mesophilic Syntrophic Acetate Oxidising Bacterium Syntrophaceticus schinkii.

Directory of Open Access Journals (Sweden)

Shahid Manzoor

Full Text Available Syntrophaceticus schinkii is a mesophilic, anaerobic bacterium capable of oxidising acetate to CO2 and H2 in intimate association with a methanogenic partner, a syntrophic relationship which operates close to the energetic limits of microbial life. Syntrophaceticus schinkii has been identified as a key organism in engineered methane-producing processes relying on syntrophic acetate oxidation as the main methane-producing pathway. However, due to strict cultivation requirements and difficulties in reconstituting the thermodynamically unfavourable acetate oxidation, the physiology of this functional group is poorly understood. Genome-guided and whole transcriptome analyses performed in the present study provide new insights into habitat adaptation, syntrophic acetate oxidation and energy conservation. The working draft genome of Syntrophaceticus schinkii indicates limited metabolic capacities, with lack of organic nutrient uptake systems, chemotactic machineries, carbon catabolite repression and incomplete biosynthesis pathways. Ech hydrogenase, [FeFe] hydrogenases, [NiFe] hydrogenases, F1F0-ATP synthase and membrane-bound and cytoplasmic formate dehydrogenases were found clearly expressed, whereas Rnf and a predicted oxidoreductase/heterodisulphide reductase complex, both found encoded in the genome, were not expressed under syntrophic growth condition. A transporter sharing similarities to the high-affinity acetate transporters of aceticlastic methanogens was also found expressed, suggesting that Syntrophaceticus schinkii can potentially compete with methanogens for acetate. Acetate oxidation seems to proceed via the Wood-Ljungdahl pathway as all genes involved in this pathway were highly expressed. This study shows that Syntrophaceticus schinkii is a highly specialised, habitat-adapted organism relying on syntrophic acetate oxidation rather than metabolic versatility. By expanding its complement of respiratory complexes, it might overcome

Biomimetic Structural Materials: Inspiration from Design and Assembly.

Science.gov (United States)

Yaraghi, Nicholas A; Kisailus, David

2018-04-20

Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

Biomimetic Structural Materials: Inspiration from Design and Assembly

Science.gov (United States)

Yaraghi, Nicholas A.; Kisailus, David

2018-04-01

Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

International Nuclear Information System (INIS)

Bukur, Dragomir B.; Lang, X.; Chokkaram, S.; Nowicki, L.; Wei, G.; Ding, Y.; Reddy, B.; Xiao, S.

1999-01-01

Despite the current worldwide oil glut, the US will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer-Tropsch (F-T) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Some of the F-T catalysts synthesized and tested at Texas A and M University under DOE Contract No. DE-AC22-89PC89868 were more active than any other known catalysts developed for maximizing production of high molecular weight hydrocarbons (waxes). The objectives of the present contract were to demonstrate repeatability of catalyst performance and reproducibility of preparation procedures of two of these catalysts on a laboratory scale. Improvements in the catalyst performance were attempted through the use of: (a) higher reaction pressure and gas space velocity to maximize the reactor productivity; (b) modifications in catalyst preparation steps; and (c) different pretreatment procedures. Repeatability of catalyst performance and reproducibility of catalyst synthesis procedure have been successfully demonstrated in stirred tank slurry reactor tests. Reactor space-time-yield was increased up to 48% by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while maintaining the gas contact time and synthesis gas conversion at a constant value. Use of calcination temperatures above 300 C, additional CaO promoter, and/or potassium silicate as the source of potassium promoter, instead of potassium bicarbonate, did not result in improved catalyst performance. By using different catalyst activation procedures they were able to increase substantially the catalyst activity, while maintaining low methane and gaseous hydrocarbon selectivities. Catalyst productivity in runs SA-0946 and SA-2186 was 0.71 and 0.86 gHC/g-Fe/h, respectively, and this represents 45-75% improvement in productivity relative to that achieved in Rheinpreussen's demonstration plant

Induction of enhanced methane oxidation in compost: Temperature and moisture response

International Nuclear Information System (INIS)

Mor, Suman; Visscher, Alex de; Ravindra, Khaiwal; Dahiya, R.P.; Chandra, A.; Cleemput, Oswald van

2006-01-01

Landfilling is one of the most common ways of municipal solid waste disposal. Degradation of organic waste produces CH 4 and other landfill gases that significantly contribute to global warming. However, before entering the atmosphere, part of the produced CH 4 can be oxidised while passing through the landfill cover. In the present study, the oxidation rate of CH 4 was studied with various types of compost as possible landfill cover. The influence of incubation time, moisture content and temperature on the CH 4 oxidation capacity of different types of compost was examined. It was observed that the influence of moisture content and temperature on methane oxidation is time-dependent. Maximum oxidation rates were observed at moisture contents ranging from 45% to 110% (dry weight basis), while the optimum temperature ranged from 15 to 30 deg. C

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.

Biomimetic dentistry

OpenAIRE

Suchetana Goswami

2018-01-01

“Biomimetics” is the field of science that uses the natural system of synthesizing materials through biomimicry. This method can be widely used in dentistry for regeneration of dental structures and replacement of lost dental tissues. This is a review paper that states its scope, history, different fields of biomimetic dentistry, and its future conditions in India.

Sustainability assessment of a lightweight biomimetic ceiling structure

International Nuclear Information System (INIS)

Antony, Florian; Speck, Thomas; Speck, Olga; Grießhammer, Rainer

2014-01-01

An intensive and continuous debate centres on the question of whether biomimetics has a specific potential to contribute to sustainability. In the context of a case study, the objective of this paper is to contribute to this debate by presenting the first systematic approach to assess the sustainability of a complex biomimetic product. The object of inquiry is a lecture hall's ribbed slab. Based on criteria suggested by the Association of German Engineers (VDI), it has been verified that the slab has been correctly defined as biomimetic. Moreover, a systematic comparative product sustainability assessment has been carefully carried out. For purposes of comparison, estimated static calculations have been performed for conceivable current state-of-the-art lightweight ceiling structures. Alternative options are a hollow article slab and a pre-stressed flat slab. Besides a detailed benefit analysis and a discussion of social effects, their costs have also been compared. A particularly detailed life cycle assessment on the respective environmental impacts has also been performed. Results show that the biomimetic ribbed slab built in the 1960s is able to keep up with the current state-of-the-art lightweight solutions in terms of sustainability. These promising results encourage a systematic search for a broad range of sustainable biomimetic solutions. (paper)

MIPs and Aptamers for Recognition of Proteins in Biomimetic Sensing.

Science.gov (United States)

Menger, Marcus; Yarman, Aysu; Erdőssy, Júlia; Yildiz, Huseyin Bekir; Gyurcsányi, Róbert E; Scheller, Frieder W

2016-07-18

Biomimetic binders and catalysts have been generated in order to substitute the biological pendants in separation techniques and bioanalysis. The two major approaches use either "evolution in the test tube" of nucleotides for the preparation of aptamers or total chemical synthesis for molecularly imprinted polymers (MIPs). The reproducible production of aptamers is a clear advantage, whilst the preparation of MIPs typically leads to a population of polymers with different binding sites. The realization of binding sites in the total bulk of the MIPs results in a higher binding capacity, however, on the expense of the accessibility and exchange rate. Furthermore, the readout of the bound analyte is easier for aptamers since the integration of signal generating labels is well established. On the other hand, the overall negative charge of the nucleotides makes aptamers prone to non-specific adsorption of positively charged constituents of the sample and the "biological" degradation of non-modified aptamers and ionic strength-dependent changes of conformation may be challenging in some application.

Reduction of Nitrogen Oxides using zeolite catalysts exchanged with cobalt

International Nuclear Information System (INIS)

Garcia M, E.A.; Bustamante L, F.; Montes de C, C.

1999-01-01

The Selective Catalytic Reduction (SCR) of NOx by methane in excess oxygen was studied over several zeolite catalysts; namely cobalt loaded mordenite, ferrierite, SM-5 and the corresponding acid forms. When NO2 predominated n the NOx mixture the acid forms showed the highest N2 formation rates under dry conditions. Mordenite supported catalysts were the most active ones followed by ferrierite and ZSM-5. The most active Co-Mordenite catalyst was tested using a NOx mixture, containing mostly NO, under dry conditions and in the presence of water and SO2. The addition of 8 % water to the reaction mixture lead to a reversible deactivation, mainly at low temperatures. When the reaction mixture contained 60 ppm SO2, the N2 formation rate decreased about a half likely due to SO2 poisoning

Biomimetic membranes and methods of making biomimetic membranes

Science.gov (United States)

Rempe, Susan; Brinker, Jeffrey C.; Rogers, David Michael; Jiang, Ying-Bing; Yang, Shaorong

2016-11-08

The present disclosure is directed to biomimetic membranes and methods of manufacturing such membranes that include structural features that mimic the structures of cellular membrane channels and produce membrane designs capable of high selectivity and high permeability or adsorptivity. The membrane structure, material and chemistry can be selected to perform liquid separations, gas separation and capture, ion transport and adsorption for a variety of applications.

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

DEFF Research Database (Denmark)

Andersson, Martin; Bligaard, Thomas; Kustov, Arkadii

2006-01-01

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

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.

FY 2000 report on the results of the regional consortium R and D project - Regional consortium energy R and D field. First year report. Development of the production technology of clean hydrogen, etc. by direct methane reforming method; 2000 nendo chiiki consortium kenkyu kaihatsu jigyo - chiiki consortium energy kenkyu kaihatsu bun'ya. Methane chokusetsu kaishitsuho ni yoru clean suiso nado no seizo gijutsu kaihatsu (dai 1 nendo) seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-03-01

The development was proceeded with of the hydrogen production method using the zeolite-base methane dehydrogenation cyclization catalyst with the specific porous structure. In this production method, there is no emission of process CO2, and hydrogen can be produced by supply of energy of 1/10 of that in the conventional technology. In FY 2000, the following were conducted: 1) conceptual design of a demonstrative experiment plant; 2) development of catalyst processing technology; 3) development of element technology such as improvement of catalyst performance. In 1), design/specifications for demonstrative experiment use plant were fixed by design estimation and process analysis using the mid-term fluidized bed experiment device. It was decided that the mid-term fluidized bed experiment device will be constructed to evaluate the methane reforming performance of catalyst and that the reaction tower should be the stationary fluidized bed type. In 2), a catalyst activity experimental device 100 times as large as the laboratory was fabricated to evaluate the catalyst performance. By optimization of reaction conditions and preparation of the catalyst composition, the targeted catalyst system was obtained. (NEDO)

Solute redistribution studies in oxidised zirconium alloys

Energy Technology Data Exchange (ETDEWEB)

Khera, S K; Kale, G B; Gadiyar, H S [Bhabha Atomic Research Centre, Bombay (India). Metallurgy Div.

1977-01-01

Electron microprobe studies on solute distribution in oxide layers and in the regions near oxide metal interface have been carried out in the case of zircaloy-2 and zirconium binary alloys containing niobium, tin, iron, copper, chromium and nickel and oxidised in steam at 550 deg C. In the case of alloys having higher oxidation rates, the oxide of solute element was found to dissolve in ZrO/sub 2/ without any composition variation. However, for solute addition with limited solubility like Cr, Cu and Fe, solute enrichment at metal/oxide interface and depletion of the same matrix has been observed. The intensity profiles for nickel distribution were also found to be identical to Fe or Cr distribution. The mode of solute distribution has been discussed in relation to oxidation behaviour of these alloys.

Study of the morphology of corrosion features of natural graphite oxidised by dry and humid air

International Nuclear Information System (INIS)

Senevat, Jean

1965-12-01

The author reports a study which aimed at highlighting the morphology differences between corrosion features which affect flakes of natural graphite oxidised by dry air and by humid air. The study is based on observations made by optical and transmission electronic microscopy, this last one being performed on replicates. As the so-called 'Hennig' replicates did not result in a sufficient resolution of corrosion feature details, another method has been developed. Three classes of samples (in relationship with the rate of impurities present in samples) have been studied. Flakes have thus been sorted and each flake has then been oxidised at different wear rates. This highlights the influence of damages created by impurities in the lattice [fr

Biomimetics: The early years | Michael | Annals of Ibadan ...

African Journals Online (AJOL)

Biomimetics is a relatively new term and an evolving discipline with the potentials for transforming every aspect of medicine. Biomimetics or biomimicry is the imitation of the models, systems, and elements of nature for the purpose of solving complex biological puzzles. Insights into biological processes have already resulted ...

Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

Energy Technology Data Exchange (ETDEWEB)

Lawal, Adeniyi [Stevens Inst. of Technology, Hoboken, NJ (United States); Manganaro, James [Anasyn LLC, Princeton, NJ (United States); Goodall, Brian [Valicor Renewables LLC, Dexter, MI (United States); Farrauto, Robert [Columbia Univ., New York, NY (United States)

2015-03-24

catalysts, and consumes less hydrogen, if methanation can be mitigated. Our methanation data on Pt and Rh indicate effective suppression of methanation. Our data also show that our catalysts are less susceptible to coking; and unlike NiMo and CoMo, precious metal catalysts are not deactivated by water, a by-product of HDO of algae oil. Finally, our catalysts do not need to be sulfided to be active. A rigorous techno-economic analysis of our process for commercial scale production of 10,000 barrels per day of hydrotreated algae oil, with nutraceuticals co-product claiming only 0.05% of the raw algae oil, indicates an estimated plant gate price of ~$10/gal. Sensitivity analysis shows that critical parameters affecting sale price include (1) algae doubling time (2) biomass oil content (3) CAPEX, and (4) moisture content of post extracted algae residue. Modest improvements in these areas will result in enhanced and competitive economics. Based on a life cycle assessment for greenhouse gas emission, we found that if algae oil replaced 10% of the US consumption, this would result in a CO2e reduction of 210,000 tons per day. Improving the drying process for animal feed by 50% would result in further significant reduction in CO2e.

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)

Catalytic and Noncatalytic Conversion of Methane to Olefins and Synthesis Gas in an AC Parallel Plate Discharge Reactor

Directory of Open Access Journals (Sweden)

Mohammad Ali Khodagholi

2013-01-01

Full Text Available Direct conversion of methane to ethylene, acetylene, and synthesis gas at ambient pressure and temperature in a parallel plate discharge reactor was investigated. The experiments were carried out using a quartz reactor of outer diameter of 9 millimeter and a driving force of ac current of 50 Hz. The input power to the reactor to establish a stable gas discharge varied from 9.6 to maximum 15.3 watts (w. The effects of ZSM5, Fe–ZSM5, and Ni–ZSM5 catalysts combined with corona discharge for conversion of methane to more valued products have been addressed. It was found that in presence or absence of a catalyst in gas discharge reactor, the rate of methane and oxygen conversion increased upon higher input power supplied to the reactor. The effect of Fe–ZSM5 catalyst combined with gas discharge plasma yields C2 hydrocarbons up to 21.9%, which is the highest productions of C2 hydrocarbons in this work. The effect of combined Ni–ZSM5 and gas discharge plasma was mainly production of synthesis gas. The advantage of introducing ZSM5 to the plasma zone was increase in synthesis gas and acetylene production. The highest energy efficiency was 0.22 mmol/kJ, which belongs to lower rate of energy injection to the reactor.

Biomimetics: nature based innovation

National Research Council Canada - National Science Library

Bar-Cohen, Yoseph

2012-01-01

"Based on the concept that nature offers numerous sources of inspiration for inventions related to mechanisms, materials, processes, and algorithms, this book covers the topic of biomimetics and the inspired innovation...

Biomimetic dentistry

Directory of Open Access Journals (Sweden)

Suchetana Goswami

2018-01-01

Full Text Available “Biomimetics” is the field of science that uses the natural system of synthesizing materials through biomimicry. This method can be widely used in dentistry for regeneration of dental structures and replacement of lost dental tissues. This is a review paper that states its scope, history, different fields of biomimetic dentistry, and its future conditions in India.

Hydrothermal Gasification Of Synthetic Liquefied Wood To Methane

Energy Technology Data Exchange (ETDEWEB)

Waldner, M.H.; De Boni, E.; Vogel, F.

2005-03-01

Biomass can be effectively converted to synthetic natural gas (SNG) in a hydrothermal environment. Lower temperatures favor the production of methane rather than hydrogen. At around 420 C, catalysts are needed to ensure reasonable rates of reaction. They are tested in a new rig in terms of activity, selectivity and stability. Gold-plated surfaces ensure no interference from the stainless steel. Experiments were carried out using different feeds, such as ethanol and synthetic liquefied wood. (author)

Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

Science.gov (United States)

Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-01-01

Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

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.

Methane from landfills in Sweden. Final report; Metan fraan avfallsupplag i Sverige. Slutrapport

Energy Technology Data Exchange (ETDEWEB)

Samuelsson, Jerker [Chalmers Univ. of Technology, Goeteborg (Sweden); Galle, Bo; Boerjesson, Gunnar [Linkoeping Univ. (Sweden). Dept. of Water and Environmental Studies

2006-01-15

Three years of measurements has been conducted at seven Swedish landfills, quantifying methane emission, methane oxidation and methane production. The measurements reveal a large span between the sites in terms of gas recovery efficiency, 29-78% during normal operation. The fraction of the totally produced methane that is eventually leaking out to the atmosphere, was found to vary between 21-68%. Regarding methane oxidation, the study shows that of the methane going from the landfill interior towards the atmosphere, 6-43% is oxidised to CO{sub 2} in the different landfill cover soils. The highest methane oxidation was found in closed landfills during summertime, and the lowest at active landfills during wintertime, due to the strong temperature dependence of the oxidation. The equipment developed for methane emission measurements is based on time resolved concentration measurements with FTIR spectroscopy in combination with tracer gas releases from the surface of the landfill. The method has proven to be able to state the methane emission from the landfills with high accuracy, {+-}18% of the emission estimate (95% confidence interval). This is in line with what has been achieved in the literature for fugitive emission sources. The system has also proven to be useful for on site leak search. The precision for the methane production measurement was demonstrated to be high, down to {+-}4.2%. This enables trend studies and verification of improvement measures taken at the landfill sites. In terms of absolute accuracy for the production estimate, a 95%-confidence interval of down to (-6.0%, +6.2%) has been achieved. At times of strong methane oxidation the uncertainties increase, particularly if the emission is high. The gas production at the landfill site is therefore preferably measured during autumn-winter-spring when the temperature and the methane oxidation are low. The methane oxidation has been measured by carbon isotope technique, utilising the enrichment in

High-Titer Methane from Organosolv-Pretreated Spruce and Birch

Directory of Open Access Journals (Sweden)

Leonidas Matsakas

2017-02-01

Full Text Available The negative impact of fossil fuels and the increased demand for renewable energy sources has led to the use of novel raw material sources. Lignocellulosic biomass could serve as a possible raw material for anaerobic digestion and production of biogas. This work is aimed at using forest biomass, both softwood (spruce and hardwood (birch, as a raw material for anaerobic digestion. We examined the effect of different operational conditions for the organosolv pretreatment (ethanol content, duration of treatment, and addition of acid catalyst on the methane yield. In addition, we investigated the effect of addition of cellulolytic enzymes during the digestion. We found that inclusion of an acid catalyst during organosolv pretreatment improved the yields from spruce, but it did not affect the yields from birch. Shorter duration of treatment was advantageous with both materials. Methane yields from spruce were higher with lower ethanol content whereas higher ethanol content was more beneficial for birch. The highest yields obtained were 185 mL CH4/g VS from spruce and 259.9 mL CH4/g VS from birch. Addition of cellulolytic enzymes improved these yields to 266.6 mL CH4/g VS and 284.2 mL CH4/g VS, respectively.

Laser technology in biomimetics basics and applications

CERN Document Server

Belegratis, Maria

2013-01-01

Lasers are progressively more used as versatile tools for fabrication purposes. The wide range of available powers, wavelengths, operation modes, repetition rates etc. facilitate the processing of a large spectrum of materials at exceptional precision and quality. Hence, manifold methods were established in the past and novel methods are continuously under development. Biomimetics, the translation from nature-inspired principles to technical applications, is strongly multidisciplinary. This field offers intrinsically a wide scope of applications for laser based methods regarding structuring and modification of materials. This book is dedicated to laser fabrication methods in biomimetics. It introduces both, a laser technology as well as an application focused approach.  The book covers the most important laser lithographic methods and various biomimetics application scenarios ranging from coatings and biotechnology to construction, medical applications and photonics.

Biomimetics: forecasting the future of science, engineering, and medicine

Directory of Open Access Journals (Sweden)

Hwang J

2015-09-01

Full Text Available Jangsun Hwang,1 Yoon Jeong,1,2 Jeong Min Park,3 Kwan Hong Lee,1,2,4 Jong Wook Hong,1,2 Jonghoon Choi1,2 1Department of Bionano Technology, Graduate School, Hanyang University, Seoul, 2Department of Bionano Engineering, Hanyang University ERICA, Ansan, Korea; 3Department of Biomedical Engineering, Boston University, 4OpenView Venture Partners, Boston, MA, USA Abstract: Biomimetics is the study of nature and natural phenomena to understand the principles of underlying mechanisms, to obtain ideas from nature, and to apply concepts that may benefit science, engineering, and medicine. Examples of biomimetic studies include fluid-drag reduction swimsuits inspired by the structure of shark’s skin, velcro fasteners modeled on burrs, shape of airplanes developed from the look of birds, and stable building structures copied from the backbone of turban shells. In this article, we focus on the current research topics in biomimetics and discuss the potential of biomimetics in science, engineering, and medicine. Our report proposes to become a blueprint for accomplishments that can stem from biomimetics in the next 5 years as well as providing insight into their unseen limitations. Keywords: biomimicry, tissue engineering, biomaterials, nature, nanotechnology, nanomedicine

Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

Science.gov (United States)

Wendlandt, Alison E; Stahl, Shannon S

2014-01-08

Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

The Synergy Effect of Ni-M (M = Mo, Fe, Co, Mn or Cr Bicomponent Catalysts on Partial Methanation Coupling with Water Gas Shift under Low H2/CO Conditions

Directory of Open Access Journals (Sweden)

Xinxin Dong

2017-02-01

Full Text Available Ni-M (M = Mo, Fe, Co, Mn or Cr bicomponent catalysts were prepared through the co-impregnation method for upgrading low H2/CO ratio biomass gas into urban gas through partial methanation coupling with water gas shift (WGS. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction (XRD, H2 temperature programmed reduction (H2-TPR, H2 temperature programmed desorption (H2-TPD, scanning electron microscopy (SEM and thermogravimetry (TG. The catalytic performances demonstrated that Mn and Cr were superior to the other three elements due to the increased fraction of reducible NiO particles, promoted dispersion of Ni nanoparticles and enhanced H2 chemisorption ability. The comparative study on Mn and Cr showed that Mn was more suitable due to its smaller carbon deposition rate and wider adaptability to various H2/CO and H2O/CO conditions, indicating its better synergy effect with Ni. A nearly 100 h, the lifetime test and start/stop cycle test further implied that 15Ni-3Mn was stable for industrial application.

Cyclic process for producing methane in a tubular reactor with effective heat removal

Science.gov (United States)

Frost, Albert C.; Yang, Chang-Lee

1986-01-01

Carbon monoxide-containing gas streams are converted to methane by a cyclic, essentially two-step process in which said carbon monoxide is disproportionated to form carbon dioxide and active surface carbon deposited on the surface of a catalyst, and said carbon is reacted with steam to form product methane and by-product carbon dioxide. The exothermic heat of reaction generated in each step is effectively removed during each complete cycle so as to avoid a build up of heat from cycle-to-cycle, with particularly advantageous techniques being employed for fixed bed, tubular and fluidized bed reactor operations.

Evaluation of alternatives of exothermic methanization cycle for combined electricity and heat generation

International Nuclear Information System (INIS)

Balajka, J.; Princova, H.

1987-01-01

The possibilities are discussed of using the ADAM-EVA system for remote heat supply from nuclear heat sources to district heating systems. Attention is devoted to the use of the exothermal methanization process (ADAM station) for the combined power and heat production, this making use of the existing hot water power distribution network. The basic parameter for the evaluation of the over-all efficiency of the combined power and heat production is the maximum methanization cycle temperature which depends on the life of the methanization catalyst. Upon temperature drop below 550 degC, the conversion process can only be secured by means of two-stage methanization, which leads to a simplification of the cycle and a reduction in investment cost. At a temperature lower than 500 degC, combined power and heat production cannot be implemented. On the contrary, a considerable amount of electric power supplied from outside the system would be needed for compression work. (Z.M.)

Conversion of hot coke oven gas into light fuel gas over Ni/Al{sub 2}O{sub 3} catalyst

Energy Technology Data Exchange (ETDEWEB)

Li, L.Y.; Morishita, K.; Takarada, T. [Gunma University, Gunma (Japan). Dept. of Biology & Chemical Engineering

2006-04-15

Conversion of hot coke oven gas (COG, containing tarry material) into light fuel gas over a Ni/Al{sub 2}O{sub 3} catalyst was studied. Laboratory scale tests were carried out in a two-stage fixed-bed reactor at ambient pressure. The nickel catalyst promoted the hydropyrolysis reaction of tarry materials. High yields of total product gas and methane were obtained at high hydrogen concentrations. If the hydrogen supply was adequate for hydropyrolysis of the tarry material, conversion of coal volatiles was high, at more than 95% on carbon balance, even with a gas residence time as short as 0.15 s in the catalyst bed. The product gas yield depended on catalytic temperature. At 923 K, the maximum conversion of coal volatiles into the light gas was achieved at 95.0% on carbon balance, with methane 86.7 vol% of the carbonaceous gas product. Although carbon deposits deactivated the catalyst after a long period of use, the catalyst could be regenerated by treatment with oxygen at 800 K, providing high activity in subsequent decomposition of tarry material. The influence of sulphide on the tarry material decomposition reaction was small even in a 2000 ppm H{sub 2}S atmosphere.

Fe/MCM-41 sylilated catalyst: structural changes determination during the Fischer-Tropsch reaction

International Nuclear Information System (INIS)

Bengoa, J. F.; Fellenz, N. A.; Cagnoli, M. V.; Cano, L. A.; Gallegos, N. G.; Alvarez, A. M.; Marchetti, S. G.

2010-01-01

Two Fe/MCM-41 systems, one of them sylilated, were obtained to be used as catalysts in Fischer-Tropsch reaction. They have more than 90% of the iron species located inside the support channels, leading to a narrow crystal size distribution accessible to reactive gases. The samples were characterized by X-ray diffraction, atomic absorption spectroscopy, N 2 adsorption, Moessbauer spectroscopy and Fourier transformer infrared spectroscopy. Moessbauer spectroscopy allowed us to demonstrate that the catalytic active species were the same in both catalysts. The only difference between them was the surface hydrophobicity, which decreases the 'water gas shift reaction' in the sylilated catalyst. Besides, this solid is more active for hydrocarbon production, with a lower methane yield.

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)

Amelogenin and Enamel Biomimetics

Science.gov (United States)

Ruan, Qichao; Moradian-Oldak, Janet

2015-01-01

Mature tooth enamel is acellular and does not regenerate itself. Developing technologies that rebuild tooth enamel and preserve tooth structure is therefore of great interest. Considering the importance of amelogenin protein in dental enamel formation, its ability to control apatite mineralization in vitro, and its potential to be applied in fabrication of future bio-inspired dental material this review focuses on two major subjects: amelogenin and enamel biomimetics. We review the most recent findings on amelogenin secondary and tertiary structural properties with a focus on its interactions with different targets including other enamel proteins, apatite mineral, and phospholipids. Following a brief overview of enamel hierarchical structure and its mechanical properties we will present the state-of-the-art strategies in the biomimetic reconstruction of human enamel. PMID:26251723

SHS-produced intermetallides as catalysts for hydrocarbons synthesis from CO and H{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Eliseev, O.L.; Kazantsev, R.V.; Davydov, P.E.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry; Borshch, V.N.; Pugacheva, E.V. [Russian Academy of Sciences, Chernogolovka (Russian Federation). Inst. of Structural Macrokinetics and Materials Science

2012-07-01

Raney-type polymetallic alloys were prepared by Self-Propagating High-Temperature Synthesis followed by alkaline treating. Surface morphology and composition of were studied using XRD, BET, SEM and EMPA techniques. The samples were tested in Fischer-Tropsch synthesis demonstrated rather high activity and very high selectivity to heavy paraffins. High selectivity to C{sub 5+} hydrocarbons is attributed to high thermal conductivity of alloys which prevents hot spots formation and therefore suppresses formation of methane and light hydrocarbons. Selectivity can be further improved by adding some d-metals in catalyst composition. Promotion with La seems to be particularly suitable for lowering methane formation while doping with Ni enhances methane yield greatly. (orig.)

The synthesis of higher alcohols from CO2 hydrogenation with Co, Cu, Fe-based catalysts

International Nuclear Information System (INIS)

Ji, Qinqin

2017-01-01

CO 2 is a clean carbon source for the chemical reactions, many researchers have studied the utilization of CO 2 . Higher alcohols are clean fuel additives. The synthesis of higher alcohols from CO hydrogenation has also been studied by many researchers, but there are few literatures about the synthesis of higher alcohols from CO 2 hydrogenation, which is a complex and difficult reaction. The catalysts that used for higher alcohols synthesis need at least two active phases and good cooperation. In our study, we tested the Co. Cu. Fe spinel-based catalysts and the effect of supports (CNTs and TUD-1) and promoters (K, Na, Cs) to the HAS reaction. We found that catalyst CuFe-precursor-800 is beneficial for the synthesis of C2+ hydrocarbons and higher alcohols. In the CO 2 hydrogenation, Co acts as a methanation catalyst rather than acting as a FT catalyst, because of the different reaction mechanism between CO hydrogenation and CO 2 hydrogenation. In order to inhibit the formation of huge amount of hydrocarbons, it is better to choose catalysts without Co in the CO 2 hydrogenation reaction. Compared the functions of CNTs and TUD-1, we found that CNTs is a perfect support for the synthesis of long-chain products (higher alcohols and C2+ hydrocarbons). The TUD-1 support are more suitable for synthesis of single-carbon products (methane and methanol).The addition of alkalis as promoters does not only lead to increase the conversion of CO 2 and H 2 , but also sharply increased the selectivity to the desired products, higher alcohols. The catalyst 0.5K30CuFeCNTs owns the highest productivities (370.7 g.kg -1 .h -1 ) of higher alcohols at 350 C and 50 bar. (author) [fr

Biomimetics materials, structures and processes : examples, ideas and case studies

CERN Document Server

Bruckner, Dietmar; Hellmich, Christian; Schmiedmayer, Heinz-Bodo; Stachelberger, Herbert; Gebeshuber, Ille

2011-01-01

The book presents an outline of current activities in the field of biomimetics and integrates a variety of applications comprising biophysics, surface sciences, architecture and medicine. Biomimetics as innovation method is characterised by interdisciplinary information transfer from the life sciences to technical application fields aiming at increased performance, functionality and energy efficiency. The contributions of the book relate to the research areas: - Materials and structures in nanotechnology and biomaterials - Biomimetic approaches to develop new forms, construction principles and design methods in architecture - Information and dynamics in automation, neuroinformatics and biomechanics Readers will be informed about the latest research approaches and results in biomimetics with examples ranging from bionic nano-membranes to function-targeted design of tribological surfaces and the translation of natural auditory coding strategies.

Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

KAUST Repository

Khan, Abdulaziz M.

2016-01-01

the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized

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.

Influence of surface topography on the surface durability of steam oxidised sintered iron

Directory of Open Access Journals (Sweden)

José Daniel Biasoli de Mello

2005-06-01

Full Text Available Durability of surfaces has been reported as the main factor affecting tribological behavior of steam oxidised sintered iron. The presence of surface pores and their negative influence on load bearing capacity, suggest that surface topography might play an important role on the durability of the oxide layer. In this paper, the influence of compaction pressure and powder grade on surface topography, and as a consequence, its effect on the tribological behavior of steam oxidised sintered iron has been analysed. Specimens prepared from atomised iron powders with different sizes were compacted using 4 different pressures, sintered, and then subjected to steam treatment. Tribological characterisation was carried out in a reciprocating sliding wear test. Although the processing parameters affected the surface topography to a considerable extent, the main influence may be attributed to powder grade. A strong influence of surface topography on the durability distance, evaluated in terms of the evolution of contact resistance with total sliding distance, has been highlighted. Surfaces which were smoother and had high load-carrying capacity were always associated with a higher durability distance.

Methanation process utilizing split cold gas recycle

Science.gov (United States)

Tajbl, Daniel G.; Lee, Bernard S.; Schora, Jr., Frank C.; Lam, Henry W.

1976-07-06

In the methanation of feed gas comprising carbon monoxide and hydrogen in multiple stages, the feed gas, cold recycle gas and hot product gas is mixed in such proportions that the mixture is at a temperature sufficiently high to avoid carbonyl formation and to initiate the reaction and, so that upon complete reaction of the carbon monoxide and hydrogen, an excessive adiabatic temperature will not be reached. Catalyst damage by high or low temperatures is thereby avoided with a process that utilizes extraordinarily low recycle ratios and a minimum of investment in operating costs.

Influence of Cobalt Precursor on Efficient Production of Commercial Fuels over FTS Co/SiC Catalyst

Directory of Open Access Journals (Sweden)

Ana Raquel de la Osa

2016-07-01

Full Text Available β-SiC-supported cobalt catalysts have been prepared from nitrate, acetate, chloride and citrate salts to study the dependence of Fischer–Tropsch synthesis (FTS on the type of precursor. Com/SiC catalysts were synthetized by vacuum-assisted impregnation while N2 adsorption/desorption, XRD, TEM, TPR, O2 pulses and acid/base titrations were used as characterization techniques. FTS catalytic performance was carried out at 220 °C and 250 °C while keeping constant the pressure (20 bar, space velocity (6000 Ncm3/g·h and syngas composition (H2/CO:2. The nature of cobalt precursor was found to influence basic behavior, extent of reduction and metallic particle size. For β-SiC-supported catalysts, the use of cobalt nitrate resulted in big Co crystallites, an enhanced degree of reduction and higher basicity compared to acetate, chloride and citrate-based catalysts. Consequently, cobalt nitrate provided a better activity and selectivity to C5+ (less than 10% methane was formed, which was centered in kerosene-diesel fraction (α = 0.90. On the contrary, catalyst from cobalt citrate, characterized by the highest viscosity and acidity values, presented a highly dispersed distribution of Co nanoparticles leading to a lower reducibility. Therefore, a lower FTS activity was obtained and chain growth probability was shortened as observed from methane and gasoline-kerosene (α = 0.76 production when using cobalt citrate.

Biomimetic chemical sensors using bioengineered olfactory and taste cells.

Science.gov (United States)

Du, Liping; Zou, Ling; Zhao, Luhang; Wang, Ping; Wu, Chunsheng

2014-01-01

Biological olfactory and taste systems are natural chemical sensing systems with unique performances for the detection of environmental chemical signals. With the advances in olfactory and taste transduction mechanisms, biomimetic chemical sensors have achieved significant progress due to their promising prospects and potential applications. Biomimetic chemical sensors exploit the unique capability of biological functional components for chemical sensing, which are often sourced from sensing units of biological olfactory or taste systems at the tissue level, cellular level, or molecular level. Specifically, at the cellular level, there are mainly two categories of cells have been employed for the development of biomimetic chemical sensors, which are natural cells and bioengineered cells, respectively. Natural cells are directly isolated from biological olfactory and taste systems, which are convenient to achieve. However, natural cells often suffer from the undefined sensing properties and limited amount of identical cells. On the other hand, bioengineered cells have shown decisive advantages to be applied in the development of biomimetic chemical sensors due to the powerful biotechnology for the reconstruction of the cell sensing properties. Here, we briefly summarized the most recent advances of biomimetic chemical sensors using bioengineered olfactory and taste cells. The development challenges and future trends are discussed as well.

Reaction in air and in nitrogen of pre-oxidised Zircaloy-4 and M5™ claddings

Energy Technology Data Exchange (ETDEWEB)

Duriez, C., E-mail: christian.duriez@irsn.fr [Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PSN-RES/SEREX-LE2M, Centre de Cadarache, St Paul-Lez-Durance 13115 (France); Drouan, D. [Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PSN-RES/SEREX-LE2M, Centre de Cadarache, St Paul-Lez-Durance 13115 (France); Pouzadoux, G. [Université Technologique de Troyes, BP 2060, Troyes 10010 (France)

2013-10-15

High temperature reactivity in air and in nitrogen of pre-oxidised Zircaloy-4 and M5™ claddings has been studied by thermogravimetry. Claddings were pre-oxidised at low temperature with the aim of simulating spent fuel. Different pre-oxidation modes, inducing significant variation in the pre-oxides microstructure, were compared. The behaviour in air, investigated in the 850–1000 °C temperature range, was found to be strongly dependant on the type of pre-oxide: the compact pre-oxide formed in autoclave (at temperature, pressure, and water chemistry representative of PWR conditions) significantly slows down the degradation in air compared to the bare alloys; on the contrary, a pre-oxide formed at 500 °C at ambient pressure, either in oxygen or in steam, favours the initiation of post-breakaway type oxidation, which in air is associated with nitride formation. The behaviour in nitrogen has been investigated in the 800–1200 °C temperature range, with Zircaloy-4 pre-oxidised at 500 °C in O{sub 2}. Reactivity is low up to 1000 °C but becomes very significant at the highest temperatures investigated, 1100 and 1200 °C. Finally, cladding segments first reacted in N{sub 2} at 1100 °C, were exposed to air and show fast oxidation even at the lowest temperature investigated (600 °C)

Biomimetic Materials for Pathogen Neutralization

National Research Council Canada - National Science Library

Ingber, Donald

1997-01-01

...) and polymer chemistry fabrication technologies for the production of synthetic 'biomimetic' materials that exhibit the mechanical responsiveness and biochemical processing capabilities of living cells and tissues...

Methanation of carbon oxides. History, status quo and future perspectives

Energy Technology Data Exchange (ETDEWEB)

Kaltner, W.; Rakoczy, R.A. [Clariant SE, Muenchen (Germany)

2012-07-01

With increasing demand in fossil sources and especially crude oil based energy carrier, proven reserves will be diminishing. Besides alternative and sustainable sources the conversion of coal into fuels which can be distributed within the existing infrastructure becomes extremely important in areas of fast growing energy demand. Driver for these technologies is mostly the lack of crude oil and availability of coal like in China or South Africa. The most common way to convert coal into chemicals and fuels is the gasification to yield a gas mixture known as synthesis gas. Synthesis gas can be converted in highly pure methane used as 'substitute natural gas' (SNG) in gas grids of major cities to produce heat at home and industry. All available SNG technologies are characterized by the difficulty to control the extreme heat release of the methanation reaction. This presentation will give an overview on available gasification and methanation technologies from recent point of view. A lot of processes are already described in literature and there are pilot and real plants for methanation and especially SNG built. Moreover, a new process to produce methane from synthesis gas without the need of recycle streams and high temperatures will be introduced. This novel process developed by Foster Wheeler - using catalysts from Clariant - is called 'VESTA Process' in accordance with the Roman goddess of hearth and fire. (orig.)

Biomimetics as a design methodology – possibilities and challenges

DEFF Research Database (Denmark)

Lenau, Torben Anker

2009-01-01

Biomimetics – or bionik as it is called in parts of Europe – offer a number of promising opportunities and challenges for the designer. The paper investigates how biomimetics as a design methodology is used in engineering design by looking at examples of biological searches and highlight...

Device for manufacturing methane or synthetic gas from materials containing carbon using a nuclear reactor

International Nuclear Information System (INIS)

Jaeger, W.

1984-01-01

This invention concerns a device for manufacturing methane or synthetic gas from materials containing carbon using a nuclear reactor, where part of the carbon is gasified with hydration and the remaining carbon is converted to synthetic gas by adding steam. This synthetic gas consists mainly of H 2 , CO, CO 2 and CH 4 and can be converted to methane in so-called methanising using a nickel catalyst. The hydrogen gasifier is situated in the first of two helium circuits of a high temperature reactor, and the splitting furnace is situated in the second helium circuit, where part of the methane produced is split into hydrogen at high temperature, which is used for the hydrating splitting of another part of the material containing carbon. (orig./RB) [de

Effect of surface composition of yttrium-stabilized zirconia on partial oxidation of methane to synthesis gas.

NARCIS (Netherlands)

Zhu, J.J.; van Ommen, J.G.; Knoester, A.; Lefferts, Leonardus

2005-01-01

Catalytic partial oxidation of methane to synthesis gas (CPOM) over yttrium-stabilized zirconia (YSZ) was studied within a wide temperature window (500¿1100 °C). The catalysts were characterized by X-ray fluorescence (XRF) and low-energy ion scattering (LEIS). The influence of calcination

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].

Hydrogen production using thermocatalytic decomposition of methane on Ni30/activated carbon and Ni30/carbon black.

Science.gov (United States)

Srilatha, K; Viditha, V; Srinivasulu, D; Ramakrishna, S U B; Himabindu, V

2016-05-01

Hydrogen is an energy carrier of the future need. It could be produced from different sources and used for power generation or as a transport fuel which mainly in association with fuel cells. The primary challenge for hydrogen production is reducing the cost of production technologies to make the resulting hydrogen cost competitive with conventional fuels. Thermocatalytic decomposition (TCD) of methane is one of the most advantageous processes, which will meet the future demand, hence an attractive route for COx free environment. The present study deals with the production of hydrogen with 30 wt% of Ni impregnated in commercially available activated carbon and carbon black catalysts (samples coded as Ni30/AC and Ni30/CB, respectively). These combined catalysts were not attempted by previous studies. Pure form of hydrogen is produced at 850 °C and volume hourly space velocity (VHSV) of 1.62 L/h g on the activity of both the catalysts. The analysis (X-ray diffraction (XRD)) of the catalysts reveals moderately crystalline peaks of Ni, which might be responsible for the increase in catalytic life along with formation of carbon fibers. The activity of carbon black is sustainable for a longer time compared to that of activated carbon which has been confirmed by life time studies (850 °C and 54 sccm of methane).

Jacobsen Catalyst as a Cytochrome P450 Biomimetic Model for the Metabolism of Monensin A

Czech Academy of Sciences Publication Activity Database

Rocha, B. A.; de Oliveira, A. M.; Pazin, M.; Dorta, D.J.; Rodrigues, A.P.N.; Berretta, A.A.; Peti, A. P. F.; de Moraes, L.A.B.; Lopes, N. P.; Pospíšil, Stanislav; Gates, P. J.; Assis, M. D.

2014-01-01

Roč. 2014, č. 2014 (2014), s. 1-8 ISSN 2314-6133 Institutional support: RVO:61388971 Keywords : Monensin A * Jacobsen Catalyst Subject RIV: EE - Microbiology, Virology Impact factor: 1.579, year: 2014

Biomimetics and the case of the remarkable ragworms

Science.gov (United States)

Hesselberg, Thomas

2007-08-01

Biomimetics is a rapidly growing field both as an academic and as an applied discipline. This paper gives a short introduction to the current status of the discipline before it describes three approaches to biomimetics: the mechanism-driven, which is based on the study of a specific mechanism; the focused organism-driven, which is based on the study of one function in a model organism; and the integrative organism-driven approach, where multiple functions of a model organism provide inspiration. The first two are established approaches and include many modern studies and the famous biomimetic discoveries of Velcro and the Lotus-Effect, whereas the last approach is not yet well recognized. The advantages of the integrative organism-driven approach are discussed using the ragworms as a case study. A morphological and locomotory study of these marine polychaetes reveals their biomimetic potential, which includes using their ability to move in slippery substrates as inspiration for novel endoscopes, using their compound setae as models for passive friction structures and using their three gaits, slow crawling, fast crawling, and swimming as well as their rapid burrowing technique to provide inspiration for the design of displacement pumps and multifunctional robots.

Biomimetic microsensors inspired by marine life

CERN Document Server

Kottapalli, Ajay Giri Prakash; Miao, Jianmin; Triantafyllou, Michael S

2017-01-01

This book narrates the development of various biomimetic microelectromechanical systems (MEMS) sensors, such as pressure, flow, acceleration, chemical, and tactile sensors, that are inspired by sensing phenomenon that exist in marine life. The research described in this book is multi-faceted and combines the expertise and understanding from diverse fields, including biomimetics, microfabrication, sensor engineering, MEMS design, nanotechnology, and material science. A series of chapters examine the design and fabrication of MEMS sensors that function on piezoresistive, piezoelectric, strain gauge, and chemical sensing principles. By translating nature-based engineering solutions to artificial manmade technology, we could find innovative solutions to critical problems.

Evaporation-induced assembly of biomimetic polypeptides

International Nuclear Information System (INIS)

Keyes, Joseph; Junkin, Michael; Cappello, Joseph; Wu Xiaoyi; Wong, Pak Kin

2008-01-01

We report an evaporation assisted plasma lithography (EAPL) process for guided self-assembly of a biomimetic silk-elastinlike protein (SELP). We demonstrate the formation of SELP structures from millimeter to submicrometer range on plasma-treatment surface templates during an evaporation-induced self-assembly process. The self-assembly processes at different humidities and droplet volumes were investigated. The process occurs efficiently in a window of optimized operating conditions found to be at 70% relative humidity and 8 μl volume of SELP solution. The EAPL approach provides a useful technique for the realization of functional devices and systems using these biomimetic materials

Catalyst effects of fabrication of carbon nanotubes synthesized by chemical vapor deposition

International Nuclear Information System (INIS)

Tian, F.; Li, H.P.; Zhao, N.Q.; He, C.N.

2009-01-01

Catalytic effects of the fabrication of carbon nanotubes (CNTs) by chemical vapor deposition of methane were investigated by thermogravimetric analysis. More specifically, the total yield and thermal stability characteristics of the product were examined with respect to physicochemical characteristics of the catalyst. Three kinds of Ni/Al catalysts with 5 wt%, 10 wt% and 15 wt% Ni, respectively were employed to synthesize CNTs. It was determined that an optimal Ni content of the catalyst resulted in maximum yield and most stable product. With increasing the Ni content, the CNT yield increased but they became less stable during heat treatment in air. According to transmission electron microscopy observations, the defect sites along the walls and at the ends of the raw CNTs facilitated the thermal oxidative destruction of the CNTs.

Dry Reforming of Methane Using a Nickel Membrane Reactor

Directory of Open Access Journals (Sweden)

Jonas M. Leimert

2017-12-01

Full Text Available Dry reforming is a very interesting process for synthesis gas generation from CH 4 and CO 2 but suffers from low hydrogen yields due to the reverse water–gas shift reaction (WGS. For this reason, membranes are often used for hydrogen separation, which in turn leads to coke formation at the process temperatures suitable for the membranes. To avoid these problems, this work shows the possibility of using nickel self-supported membranes for hydrogen separation at a temperature of 800 ∘ C. The higher temperature effectively suppresses coke formation. The paper features the analysis of the dry reforming reaction in a nickel membrane reactor without additional catalyst. The measurement campaign targeted coke formation and conversion of the methane feedstock. The nickel approximately 50% without hydrogen separation. The hydrogen removal led to an increase in methane conversion to 60–90%.

Effects of Reduced and Oxidised Nitrogen on Rich-Fen Mosses: a 4-Year Field Experiment

NARCIS (Netherlands)

Paulissen, Maurice P.C.P.; Bobbink, Roland; Robat, Sandra A.; Verhoeven, Jos T.A.

2016-01-01

Dutch fens, subjected to high nitrogen (N) deposition levels with reduced N (NHy) highly dominating over oxidised N (NOx), have since the second half of the past century seen a significant decline of Scorpidium and other characteristic brown moss species, while several Sphagnum species have

MIPs and Aptamers for Recognition of Proteins in Biomimetic Sensing

Directory of Open Access Journals (Sweden)

Marcus Menger

2016-07-01

Full Text Available Biomimetic binders and catalysts have been generated in order to substitute the biological pendants in separation techniques and bioanalysis. The two major approaches use either “evolution in the test tube” of nucleotides for the preparation of aptamers or total chemical synthesis for molecularly imprinted polymers (MIPs. The reproducible production of aptamers is a clear advantage, whilst the preparation of MIPs typically leads to a population of polymers with different binding sites. The realization of binding sites in the total bulk of the MIPs results in a higher binding capacity, however, on the expense of the accessibility and exchange rate. Furthermore, the readout of the bound analyte is easier for aptamers since the integration of signal generating labels is well established. On the other hand, the overall negative charge of the nucleotides makes aptamers prone to non-specific adsorption of positively charged constituents of the sample and the “biological” degradation of non-modified aptamers and ionic strength-dependent changes of conformation may be challenging in some application.

Recent changes in carbon dioxide, carbon monoxide and methane and the implications for global climate change

Energy Technology Data Exchange (ETDEWEB)

Novelli, P.C.; Conway, T.J.; Dlugokencky, E.J.; Tans, P.P. [National Oceanic and Atmospheric Administration, Boulder, CO (United States). Climate Monitoring and Diagnostics Lab.

1995-01-01

The article reviews figures for published data on recent changes of atmospheric levels of carbon dioxide, carbon monoxide and methane in terms of their sources and sinks. The largest source of CO{sub 2} is the combustion of fossil fuels, followed by emissions from deforestation and the oxidation of CO to CO{sub 2}. Carbon monoxide has an indirect influence on the earth`s radiative balance, as if levels of CO increase, levels of OH radicals decline which affects removal of other gases oxidised by this radical, notably CH{sub 4}. Major sources of CO are fossil fuel combustion, emissions from biomass, and oxidation of atmospheric CH{sub 4} and other non-methane hydrocarbons. The latest measurements suggest the depressed growth rates of CO{sub 2}, CO and CH{sub 4} have began to recover. Reasons for this are suggested. Future monitoring of atmospheric species in laboratories around the world, coupled with information on the isotopic signature of the trace gases, will improve our understanding of possible causes for trends in these gases. This will be invaluable in making policy decisions regarding future climate change. 34 refs., 4 figs.

Technology development for iron F-T catalysts. Final report

Energy Technology Data Exchange (ETDEWEB)

Frame, R.R.; Gala, H.B.

1994-08-01

The objectives of this work were twofold. The first objective was to design and construct a pilot plant for preparing precipitated iron oxide F-T precursors and demonstrate that the rate of production from this plant is equivalent to 100 lbs/day of dried metal oxide. Secondly, these precipitates were to be used to prepare catalysts capable of achieving 88% CO + H{sub 2} conversion with {le} 5 mole percent selectivity to methane + ethane.

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.

{alpha}-Al{sub 2}O{sub 3} catalyst supports for synthesis gas production: influence of different alumina bonding agents on support and catalyst properties

Energy Technology Data Exchange (ETDEWEB)

Marturano, M. [Centro de Investigacion y Desarrollo en Procesos Cataliticos, La Plata (Argentina); Aglietti, E.F. [Centro de Tecnologia de Recursos Minerales y Ceramica (CETMIC), Gonnet (Argentina); Ferretti, O. [Centro de Investigacion y Desarrollo en Procesos Cataliticos, La Plata (Argentina)]|[Univ. Nacional de La Plata, Dept. de Ingenieria Quimica de la Facultad de Ingenieria, La Plata (Argentina)

1997-02-01

Aluminas are widely used as catalytic supports in chemical reactions. Reforming reactions to obtain synthesis gas requires good mechanical strength and low sintering behaviour. In this work, the influence of bentonite, aluminium phosphate and alumina gel as binder agents of a calcined {alpha}-Al{sub 2}O{sub 3} are analyzed with respect to support and catalytic properties. The {alpha}-Al{sub 2}O{sub 3} supports, calcined at 1300 C, are then impregnated with solutions of Ni and Al inorganic salts to obtain the catalysts and are finally tested in the reforming reaction of methane to synthesis gas at 500-900 C. Supports and catalysts are characterized by XRD, SEM, N{sub 2} adsorption, mechanical strength test and other techniques. Mechanical strength depends on the type and quantity of binder material used during support preparation. The influence of the support on the performance of the resulting catalyst is evidenced by means of catalytic tests. (orig.) 8 refs.

Biomimetic modelling.

OpenAIRE

Vincent, Julian F V

2003-01-01

Biomimetics is seen as a path from biology to engineering. The only path from engineering to biology in current use is the application of engineering concepts and models to biological systems. However, there is another pathway: the verification of biological mechanisms by manufacture, leading to an iterative process between biology and engineering in which the new understanding that the engineering implementation of a biological system can bring is fed back into biology, allowing a more compl...

Biomimetics in materials science self-healing, self-lubricating, and self-cleaning materials

CERN Document Server

Nosonovsky, Michael

2012-01-01

Biomimetics in Materials Science provides a comprehensive theoretical and practical review of biomimetic materials with self-healing, self-lubricating and self-cleaning properties. These three topics are closely related and constitute rapidly developing areas of study. The field of self-healing materials requires a new conceptual understanding of this biomimetic technology, which is in contrast to traditional  engineering processes such as wear and fatigue.  Biomimetics in Materials Science is the first monograph to be devoted to these materials. A new theoretical framework for these processes is presented based on the concept of multi-scale structure of entropy and non-equilibrium thermodynamics, together with a detailed review of the available technology. The latter includes experimental, modeling, and simulation results obtained on self-healing/lubricating/cleaning materials since their emergence in the past decade. Describes smart, biomimetic materials in the context of nanotechnology, biotechnology, an...

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)

A facile method for the preparation of Covalent Triazine Framework coated monoliths as catalyst support - applications in C1 catalysis

KAUST Repository

Bavykina, Anastasiya V.

2017-07-17

A quasi Chemical Vapour Deposition method for the manufacturing of well-defined Covalent Triazine Framework (CTF) coatings on cordierite monoliths is reported. The resulting supported porous organic polymer is an excellent support for the immobilisation of two different homogeneous catalysts: 1) an IrIIICp*-based catalyst for the hydrogen production from formic acid, and 2) a PtII-based for the direct activation of methane via Periana chemistry. The immobilised catalysts display a much higher activity in comparison with the unsupported CTF operated in slurry because of improved mass transport. Our results demonstrate that CTF based catalysts can be further optimised by engineering at different length-scales.

A facile method for the preparation of Covalent Triazine Framework coated monoliths as catalyst support - applications in C1 catalysis

KAUST Repository

Bavykina, Anastasiya V.; Olivos Suarez, Alma Itzel; Osadchii, Dmitrii; Valecha, Rahul; Franz, Robert; Makkee, Michiel; Kapteijn, Freek; Gascon, Jorge

2017-01-01

A quasi Chemical Vapour Deposition method for the manufacturing of well-defined Covalent Triazine Framework (CTF) coatings on cordierite monoliths is reported. The resulting supported porous organic polymer is an excellent support for the immobilisation of two different homogeneous catalysts: 1) an IrIIICp*-based catalyst for the hydrogen production from formic acid, and 2) a PtII-based for the direct activation of methane via Periana chemistry. The immobilised catalysts display a much higher activity in comparison with the unsupported CTF operated in slurry because of improved mass transport. Our results demonstrate that CTF based catalysts can be further optimised by engineering at different length-scales.

Bio-Mimetic Sensors Based on Molecularly Imprinted Membranes

Directory of Open Access Journals (Sweden)

Catia Algieri

2014-07-01

Full Text Available An important challenge for scientific research is the production of artificial systems able to mimic the recognition mechanisms occurring at the molecular level in living systems. A valid contribution in this direction resulted from the development of molecular imprinting. By means of this technology, selective molecular recognition sites are introduced in a polymer, thus conferring it bio-mimetic properties. The potential applications of these systems include affinity separations, medical diagnostics, drug delivery, catalysis, etc. Recently, bio-sensing systems using molecularly imprinted membranes, a special form of imprinted polymers, have received the attention of scientists in various fields. In these systems imprinted membranes are used as bio-mimetic recognition elements which are integrated with a transducer component. The direct and rapid determination of an interaction between the recognition element and the target analyte (template was an encouraging factor for the development of such systems as alternatives to traditional bio-assay methods. Due to their high stability, sensitivity and specificity, bio-mimetic sensors-based membranes are used for environmental, food, and clinical uses. This review deals with the development of molecularly imprinted polymers and their different preparation methods. Referring to the last decades, the application of these membranes as bio-mimetic sensor devices will be also reported.

Bio-Mimetic Sensors Based on Molecularly Imprinted Membranes

Science.gov (United States)

Algieri, Catia; Drioli, Enrico; Guzzo, Laura; Donato, Laura

2014-01-01

An important challenge for scientific research is the production of artificial systems able to mimic the recognition mechanisms occurring at the molecular level in living systems. A valid contribution in this direction resulted from the development of molecular imprinting. By means of this technology, selective molecular recognition sites are introduced in a polymer, thus conferring it bio-mimetic properties. The potential applications of these systems include affinity separations, medical diagnostics, drug delivery, catalysis, etc. Recently, bio-sensing systems using molecularly imprinted membranes, a special form of imprinted polymers, have received the attention of scientists in various fields. In these systems imprinted membranes are used as bio-mimetic recognition elements which are integrated with a transducer component. The direct and rapid determination of an interaction between the recognition element and the target analyte (template) was an encouraging factor for the development of such systems as alternatives to traditional bio-assay methods. Due to their high stability, sensitivity and specificity, bio-mimetic sensors-based membranes are used for environmental, food, and clinical uses. This review deals with the development of molecularly imprinted polymers and their different preparation methods. Referring to the last decades, the application of these membranes as bio-mimetic sensor devices will be also reported. PMID:25196110

Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

KAUST Repository

AlMana, Noor

2016-06-19

The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance

Biomimetic magnetic nanoparticles

OpenAIRE

Klem, Michael T.; Young, Mark; Douglas, Trevor

2005-01-01

Magnetic nanoparticles are of considerable interest because of their potential use in high-density memory devices, spintronics, and applications in diagnostic medicine. The conditions for synthesis of these materials are often complicated by their high reaction temperatures, costly reagents, and post-processing requirements. Practical applications of magnetic nanoparticles will require the development of alternate synthetic strategies that can overcome these impediments. Biomimetic approaches...

Homogenous conversion of methane to methanol. 1: Catalytic activation and functionalization of methane by cis-platin in sulfuric acid -- a density functional study of the thermochemistry

Energy Technology Data Exchange (ETDEWEB)

Mylvaganam, K.; Bacskay, G.B.; Hush, N.S. [Univ. of Sydney, New South Wales (Australia)

1999-05-19

The selective oxidation of methane to methanol or other efficiently transportable material represents one of the outstanding challenges of the chemical industry. Methane, being the dominant component of natural gas, is an abundant resource, yet in comparison with petroleum products it is currently underutilized, mainly because the transportation of a gas with a very low boiling point is expensive. The situation could change drastically if a simple, efficient, and economical method were found to convert methane to a readily transportable material such as methanol. The recent announcement by Periana et al. (Science, 1998, 280, 560) of 70% one-pass homogeneous catalysis of methane-to-methanol conversion with high selectivity in sulfuric acid solution under moderate conditions represents an important advance in the selective oxidation of alkanes, an area of considerable current interest and activity. The conversion is catalyzed by bis(2,2{prime}-bipyrimidine)Pt(II)Cl{sub 2}. In this work, the thermodynamics of the activation and functionalization steps of the related cis-platin-catalyzed process in H{sub 2}SO{sub 4} are calculated using density functional techniques, including the calculation of solvation free energies by a dielectric continuum method. It is concluded that electrophilic attack by CH{sub 4} on an intermediate which may be regarded as a tetracoordinate solvated analogue of a gas-phase, T-shaped, three-coordinate Pt(II) species, followed by oxidation of the resulting methyl complex to a methyl bisulfate ester, is thermodynamically feasible. This is in general accord with the mechanism proposed by Periana et al., but now, on the basis of the computational predictions, the nature of the active catalyst, as well as that of the intermediates, can be more precisely defined. While the alternative mechanism of oxidative addition does not appear to be thermodynamically feasible when using Pt(II) catalysts, catalysis by a Pt(IV) species is predicted to be, on

Cationic amino acids specific biomimetic silicification in ionic liquid: a quest to understand the formation of 3-D structures in diatoms.

Directory of Open Access Journals (Sweden)

Rajesh Ramanathan

Full Text Available The intricate, hierarchical, highly reproducible, and exquisite biosilica structures formed by diatoms have generated great interest to understand biosilicification processes in nature. This curiosity is driven by the quest of researchers to understand nature's complexity, which might enable reproducing these elegant natural diatomaceous structures in our laboratories via biomimetics, which is currently beyond the capabilities of material scientists. To this end, significant understanding of the biomolecules involved in biosilicification has been gained, wherein cationic peptides and proteins are found to play a key role in the formation of these exquisite structures. Although biochemical factors responsible for silica formation in diatoms have been studied for decades, the challenge to mimic biosilica structures similar to those synthesized by diatoms in their natural habitats has not hitherto been successful. This has led to an increasingly interesting debate that physico-chemical environment surrounding diatoms might play an additional critical role towards the control of diatom morphologies. The current study demonstrates this proof of concept by using cationic amino acids as catalyst/template/scaffold towards attaining diatom-like silica morphologies under biomimetic conditions in ionic liquids.

Co-generation of synthesis gas and C{sub 2+} hydrocarbons from methane and carbon dioxide in a hybrid catalytic-plasma reactor: A review

Energy Technology Data Exchange (ETDEWEB)

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

2006-03-15

The topics on conversion and utilization of methane and carbon dioxide are important issues in tackling the global warming effects from the two greenhouse gases. Several technologies including catalytic and plasma have been proposed to improve the process involving conversion and utilization of methane and carbon dioxide. In this paper, an overview of the basic principles, and the effects of CH{sub 4}/CO{sub 2} feed ratio, total feed flow rate, discharge power, catalyst, applied voltage, wall temperature, and system pressure in dielectric-barrier discharge (DBD) plasma reactor are addressed. The discharge power, discharge gap, applied voltage and CH{sub 4}/CO{sub 2} ratio in the feed showed the most significant effects on the reactor performance. Co-feeding carbon dioxide with the methane feed stream reduced coking and increased methane conversion. The H{sub 2}/CO ratio in the products was significantly affected by CH{sub 4}/CO{sub 2} ratio. The synergism of the catalyst placed in the discharge gap and the plasma affected the products distribution significantly. Methane and carbon dioxide conversions were influenced significantly by discharge power and applied voltage. The drawbacks of DBD plasma application in the CH{sub 4}-CO{sub 2} conversion should be taken into consideration before a new plausible reactor system can be implemented. 76 refs., 4 figs., 2 tabs.

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)

Tissue bionics: examples in biomimetic tissue engineering

Energy Technology Data Exchange (ETDEWEB)

Green, David W [Bone and Joint Research Group, Developmental Origins of Health and Disease, General Hospital, University of Southampton, SO16 6YD (United Kingdom)], E-mail: Hindoostuart@googlemail.com

2008-09-01

Many important lessons can be learnt from the study of biological form and the functional design of organisms as design criteria for the development of tissue engineering products. This merging of biomimetics and regenerative medicine is termed 'tissue bionics'. Clinically useful analogues can be generated by appropriating, modifying and mimicking structures from a diversity of natural biomatrices ranging from marine plankton shells to sea urchin spines. Methods in biomimetic materials chemistry can also be used to fabricate tissue engineering scaffolds with added functional utility that promise human tissues fit for the clinic.

Tissue bionics: examples in biomimetic tissue engineering

International Nuclear Information System (INIS)

Green, David W

2008-01-01

Many important lessons can be learnt from the study of biological form and the functional design of organisms as design criteria for the development of tissue engineering products. This merging of biomimetics and regenerative medicine is termed 'tissue bionics'. Clinically useful analogues can be generated by appropriating, modifying and mimicking structures from a diversity of natural biomatrices ranging from marine plankton shells to sea urchin spines. Methods in biomimetic materials chemistry can also be used to fabricate tissue engineering scaffolds with added functional utility that promise human tissues fit for the clinic

Do Biomimetic Students Think Outside the Box?