Advances in catalysts for internal reforming in high temperature fuel cells

Science.gov (United States)

Dicks, A. L.

Catalytic steam reforming of natural gas is an attractive method of producing the hydrogen required by the present generation of fuel cells. The molten carbonate (MCFC) and solid oxide (SOFC) fuel cells operate at high enough temperatures for the endothermic steam reforming reaction to be carried out within the stack. For the MCFC, the conventional anodes have insufficient activity to catalyse the steam reforming of natural gas. For these cells, internal reforming can be achieved only with the addition of a separate catalyst, preferably located in close proximity to the anode. However, in the so-called `Direct Internal Reforming' configuration, attack from alkali in the MCFC may severely limit catalyst lifetime. In the case of the state-of-the-art SOFC, natural gas can be reformed directly on the nickel cermet anode. However, in the SOFC, temperature variations in the cell caused by the reforming reaction may limit the amount of internal reforming that can be allowed in practice. In addition, some external pre-reforming may be desirable to remove high molecular weight hydrocarbons from the fuel gas, which would otherwise crack to produce elemental carbon. Degradation of the SOFC anode may also be a problem when internal reforming is carried out. This has prompted several research groups to investigate the use of alternative anode materials.

Numerical simulation of effect of catalyst wire-mesh pressure drop characteristics on flow distribution in catalytic parallel plate steam reformer

DEFF Research Database (Denmark)

Sigurdsson, Haftor Örn; Kær, Søren Knudsen

2012-01-01

Steam reforming of hydrocarbons using a catalytic plate-type-heat-exchanger (CPHE) reformer is an attractive method of producing hydrogen for a fuel cell-based micro combined-heat-and-power system. In this study the flow distribution in a CPHE reformer, which uses a coated wire-mesh catalyst...

Modification of Catalysts for Steam Reforming of Fluid Hydrocarbons. Research of Gas-Dynamic Duct Cooling Using Planar and Framework Catalysts (CD-ROM)

National Research Council Canada - National Science Library

Kuranov, Alexander L

2005-01-01

.... One way of fuel conversion is the catalytic steam reforming of hydrocarbon. This reaction has a large heat capacity and gives maximum quantity of molecular hydrogen among known reactions of hydrocarbons...

Study and modelling of deactivation by coke in catalytic reforming of hydrocarbons on Pt-Sn/Al{sub 2}O{sub 3} catalyst; La microbalance inertielle: etude et modelisation cinetique de la desactivation par le coke en reformage catalytique des hydrocarbures sur catalyseur Pt-Sn/Al{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Mathieu-Deghais, S.

2004-07-01

Catalytic reforming is the refining process that produces gasoline with a high octane number. During a reforming operation, undesired side reactions promote the formation of carbon deposits (coke) on the surface of the catalyst. As the reactions proceed, the coke accumulation leads to a progressive decrease of the catalyst activity and to a change in its selectivity. Getting this phenomenon under control is interesting to optimize the industrial plants. This work aims to improve the comprehension and the modeling of coke formation and its deactivating effect on reforming reactions, while working under conditions chosen within a range as close as possible to the industrial conditions of the regenerative process. The experimental study is carried out with a micro unit that is designed to observe simultaneously the coke formation and its influence on the catalyst activity. A vibrational microbalance reactor (TEOM - Tapered Element Oscillating Microbalance) is used to provide continuous monitoring of coke. On-line gas chromatography is used to observe the catalyst activity and selectivity as a function of the coke content. The coking experiments are performed on a fresh Pt-Sn/alumina catalyst, with mixtures of hydrocarbon molecules of 7 carbon atoms as hydrocarbon feeds. The coking tests permitted to highlight the operating parameters that may affect the amount of coke, and to identify the hydrocarbon molecules that behave as coke intermediate. A kinetic model for coke formation could be developed through the compilation of these results. The catalytic activity analysis permitted to point out the coke effect on both of the active phases of the catalyst, to construct a simplified reforming kinetic model that simulates the catalyst activity under the reforming conditions, and to quantify deactivation via deactivation functions. (author)

Autothermal reforming catalyst having perovskite structure

Science.gov (United States)

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

Steam hydrocarbon cracking and reforming

NARCIS (Netherlands)

Golombok, M.

2004-01-01

Many industrial chemical processes are taught as distinct contrasting reactions when in fact the unifying comparisons are greater than the contrasts. We examine steam hydrocarbon reforming and steam hydrocarbon cracking as an example of two processes that operate under different chemical reactivity

Short Review: Cu Catalyst for Autothermal Reforming Methanol for Hydrogen Production

Directory of Open Access Journals (Sweden)

Ho-Shing Wu

2012-06-01

Full Text Available Hydrogen is a promising alternative energy sources, hydrogen can be used in fuel cell applications to pro-ducing electrical energy and water as byproduct. Therefore, fuel cell is a simple application and environ-mentally friendly oriented technology. Recent years various methods have been conducted to produce hy-drogen. Those methods are derived from various sources such as methanol, ethanol, gasoline, hydrocarbons. This article presents a brief review a parameter process of that affects in autothermal reforming methanol use Cu-based catalysts for production of hydrogen. Copyright © 2012 BCREC UNDIP. All rights reserved.Received: 3rd January 2012; Revised: 23rd February 2012; Accepted: 28th February 2012[How to Cite: H.S. Wu, and D. Lesmana. (2012. Short Review: Cu Catalyst for Autothermal Reforming Methanol for Hydrogen Production. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 27-42. doi:10.9767/bcrec.7.1.1284.27-42][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1284.27-42 ] | View in 

Steam reforming of fuel to hydrogen in fuel cells

Science.gov (United States)

Fraioli, Anthony V.; Young, John E.

1984-01-01

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

Hydrogen production by steam reforming of liquefied natural gas over a nickel catalyst supported on mesoporous alumina xerogel

Science.gov (United States)

Seo, Jeong Gil; Youn, Min Hye; Cho, Kyung Min; Park, Sunyoung; Song, In Kyu

Mesoporous alumina xerogel (A-SG) is prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/A-SG catalyst is then prepared by an impregnation method, and is applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of the mesoporous alumina xerogel support on the catalytic performance of Ni/A-SG catalyst is investigated. For the purpose of comparison, a nickel catalyst supported on commercial alumina (A-C) is also prepared by an impregnation method (Ni/A-C). Both the hydroxyl-rich surface and the electron-deficient sites of the A-SG support enhance the dispersion of the nickel species on the support during the calcination step. The formation of the surface nickel aluminate phase in the Ni/A-SG catalyst remarkably increases the reducibility and stability of the catalyst. Furthermore, the high-surface area and the well-developed mesoporosity of the Ni/A-SG catalyst enhance the gasification of surface hydrocarbons that are adsorbed in the reaction. In the steam reforming of LNG, the Ni/A-SG catalyst exhibits a better catalytic performance than the Ni/A-C catalyst in terms of LNG conversion and hydrogen production. Moreover, the Ni/A-SG catalyst shows strong resistance toward catalyst deactivation.

Plasma-catalytic reforming of liquid hydrocarbons

International Nuclear Information System (INIS)

Nedybaliuk, O.A.; Chernyak, V.Ya; Kolgan, V.V.; Iukhymenko, V.V.; Solomenko, O.V.; Fedirchyk, I.I.; Martysh, E.V.; Demchina, V.P.; Klochok, N.V.; Dragnev, S.V.

2015-01-01

The series of experiments studying the plasma-catalytic reforming of liquid hydrocarbons was carried out. The dynamic plasma-liquid system based on a low-power rotating gliding arc with solid electrodes was used for the investigation of liquid hydrocarbons reforming process. Conversion was done via partial oxidation. A part of oxidant flow was activated by the discharge. Synthesis-gas composition was analysed by means of mass-spectrometry and gas-chromatography. A standard boiler, which operates on natural gas and LPG, was used for the burning of synthesis-gas

Methods for reformation of gaseous hydrocarbons using electrical discharge

KAUST Repository

Cha, Min Suk

2017-02-16

Methods for the reformation of gaseous hydrocarbons are provided. The methods can include forming a bubble containing the gaseous hydrocarbon in a liquid. The bubble can be generated to pass in a gap between a pair of electrodes, whereby an electrical discharge is generated in the bubble at the gap between the electrodes. The electrodes can be a metal or metal alloy with a high melting point so they can sustain high voltages of up to about 200 kilovolts. The gaseous hydrocarbon can be combined with an additive gas such as molecular oxygen or carbon dioxide. The reformation of the gaseous hydrocarbon can produce mixtures containing one or more of H2, CO, H2O, CO2, and a lower hydrocarbon such as ethane or ethylene. The reformation of the gaseous hydrocarbon can produce low amounts of CO2 and H2O, e.g. about 15 mol-% or less.

Methods for reformation of gaseous hydrocarbons using electrical discharge

KAUST Repository

Cha, Min; Zhang, Xuming

2017-01-01

Methods for the reformation of gaseous hydrocarbons are provided. The methods can include forming a bubble containing the gaseous hydrocarbon in a liquid. The bubble can be generated to pass in a gap between a pair of electrodes, whereby an electrical discharge is generated in the bubble at the gap between the electrodes. The electrodes can be a metal or metal alloy with a high melting point so they can sustain high voltages of up to about 200 kilovolts. The gaseous hydrocarbon can be combined with an additive gas such as molecular oxygen or carbon dioxide. The reformation of the gaseous hydrocarbon can produce mixtures containing one or more of H2, CO, H2O, CO2, and a lower hydrocarbon such as ethane or ethylene. The reformation of the gaseous hydrocarbon can produce low amounts of CO2 and H2O, e.g. about 15 mol-% or less.

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

Directory of Open Access Journals (Sweden)

Anna M. Venezia

2013-06-01

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

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

KAUST Repository

Takanabe, Kazuhiro

2018-01-04

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

Steam reforming of different biomass tar model compounds over Ni/Al_2O_3 catalysts

International Nuclear Information System (INIS)

Artetxe, Maite; Alvarez, Jon; Nahil, Mohamad A.; Olazar, Martin; Williams, Paul T.

2017-01-01

Highlights: • Order of reactivity: anisole > furfural > indene > phenol > toluene > methyl naphthalene. • Higher coke deposition for oxygenates (1.5–2.8%) than for aromatics (0.5–0.8%). • Amorphous coke is deposited for oxygenates and filamentous carbon for aromatics. • Ni content of 20 wt.% shows the higher conversion (90%) and H_2 potential (63%). - Abstract: This work focuses on the removal of the tar derived from biomass gasification by catalytic steam reforming on Ni/Al_2O_3 catalysts. Different tar model compounds (phenol, toluene, methyl naphthalene, indene, anisole and furfural) were individually steam reformed (after dissolving each one in methanol), as well as a mixture of all of them, at 700 °C under a steam/carbon (S/C) ratio of 3 and 60 min on stream. The highest conversions and H_2 potential were attained for anisole and furfural, while methyl naphthalene presented the lowest reactivity. Nevertheless, the higher reactivity of oxygenates compared to aromatic hydrocarbons promoted carbon deposition on the catalyst (in the 1.5–2.8 wt.% range). When the concentration of methanol is decreased in the feedstock and that of toluene or anisole is increased, the selectivity to CO is favoured in the gaseous products, thus increasing coke deposition on the catalyst and decreasing catalyst activity for the steam reforming reaction. Moreover, an increase in Ni loading in the catalyst from 5 to 20% enhances carbon conversion and H_2 formation in the steam reforming of a mixture of all the model compounds studied, but these values decrease for a Ni content of 40%. Coke formation also increased by increasing Ni loading, attaining its maximum value for 40% Ni (6.5 wt.%).

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.

Nickel catalysts for internal reforming in molten carbonate fuel cells

NARCIS (Netherlands)

Berger, R.J.; Berger, R.J.; Doesburg, E.B.M.; Doesburg, E.B.M.; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

1996-01-01

Natural gas may be used instead of hydrogen as fuel for the molten carbonate fuel cell (MCFC) by steam reforming the natural gas inside the MCFC, using a nickel catalyst (internal reforming). The severe conditions inside the MCFC, however, require that the catalyst has a very high stability. In

On the potential of nickel catalysts for steam reforming in membrane reactors

Energy Technology Data Exchange (ETDEWEB)

Pieterse, J.A.Z.; Boon, J.; Van Delft, Y.C.; Dijkstra, J.W.; Van den Brink, R.W. [Energy research Center of the Netherlands, P.O. Box 1, 1755 ZG Petten (Netherlands)

2010-10-15

Hydrogen membrane reactors have been identified as a promising option for hydrogen production for power generation from natural gas with pre-combustion decarbonisation. While Pd or Pd-alloy membranes already provide good hydrogen permeances the most suitable catalyst design for steam reforming in membrane reactors (SRMR) is yet to be identified. This contribution aims to provide insight in the suitability of nickel based catalysts in SRMR. The use of nickel (Ni) catalysts would benefit the cost-effectiveness of membrane reactors and therefore its feasibility. For this, the activity of nickel catalysts in SRMR was assessed with kinetics reported in literature. A 1D model was composed in order to compare the hydrogen production rates derived from the kinetics with the rate of hydrogen withdrawal by permeation. Catalyst stability was studied by exposing the catalysts to reformate gas with two different H/C ratios to mimic the hydrogen lean reformate gas in the membrane reactor. For both the activity (modeling) and stability study the Ni-based catalysts were compared to relevant catalyst compositions based on rhodium (Rh). Using the high pressure kinetics reported for Al2O3 supported Rh and MgAl2O4 and Al2O3 supported Ni catalyst it showed that Ni and Rh catalysts may very well provide similar hydrogen production rates. Interestingly, the stability of Ni-based catalysts proved to be superior to precious metal based catalysts under exposure to simulated reformate feed gas with low H/C molar ratio. A commercial (pre-)reforming Ni-based catalyst was selected for further testing in an experimental membrane reactor for steam reforming at high pressure. During the test period 98% conversion at 873 K could be achieved. The conversion was adjusted to approximately 90% and stable conversion was obtained during the test period of another 3 weeks. Nonetheless, carbon quantification tests of the Ni catalyst indicated that a small amount of carbon had deposited onto the catalyst

Method for the conversion of hydrocarbon charges

Energy Technology Data Exchange (ETDEWEB)

Whittam, T V

1976-11-11

The basis of the invention is the application of defined zeolites as catalysts to hydrocarbon conversion processes such as reformation, isomerization, dehydrocyclization, and cracking. By charging the zeolite carrier masses with 0.001 to 5% metal of the 8th group of the periodic system, preferably noble metals, a wide region of applications for the catalysts is achieved. A method for the isomerization of an alkyl benzene (or mixture of alkyl benzenes) in the liquid or gas phase under suitable temperature, pressure and flow-rate conditions, as well as in the presence of a cyclic hydrocarbon, is described as preferential model form of the invention; furthermore, a method for the reformation of a hydrocarbon fraction boiling in the gasoline or benzene boiling region and a method for the hydrocracking of hydrocarbon charge (e.g. naphtha, kerosine, gas oils) are given. Types of performance of the methods are explained using various examples.

Influence of Steam Reforming Catalyst Geometry on the Performance of Tubular Reformer – Simulation Calculations

Directory of Open Access Journals (Sweden)

Franczyk Ewelina

2015-06-01

Full Text Available A proper selection of steam reforming catalyst geometry has a direct effect on the efficiency and economy of hydrogen production from natural gas and is a very important technological and engineering issue in terms of process optimisation. This paper determines the influence of widely used seven-hole grain diameter (ranging from 11 to 21 mm, h/d (height/diameter ratio of catalyst grain and Sh/St (hole surface/total cylinder surface in cross-section ratio (ranging from 0.13 to 0.37 on the gas load of catalyst bed, gas flow resistance, maximum wall temperature and the risk of catalyst coking. Calculations were based on the one-dimensional pseudo-homogeneous model of a steam reforming tubular reactor, with catalyst parameters derived from our investigations. The process analysis shows that it is advantageous, along the whole reformer tube length, to apply catalyst forms of h/d = 1 ratio, relatively large dimensions, possibly high bed porosity and Sh/St ≈ 0.30-0.37 ratio. It enables a considerable process intensification and the processing of more natural gas at the same flow resistance, despite lower bed activity, without catalyst coking risk. Alternatively, plant pressure drop can be reduced maintaining the same gas load, which translates directly into diminishing the operating costs as a result of lowering power consumption for gas compression.

Hydroprocessing using regenerated spent heavy hydrocarbon catalyst

International Nuclear Information System (INIS)

Clark, F.T.; Hensley, A.L. Jr.

1992-01-01

This patent describes a process for hydroprocessing a hydrocarbon feedstock. It comprises: contacting the feedstock with hydrogen under hydroprocessing conditions with a hydroprocessing catalyst wherein the hydroprocessing catalyst contains a total contaminant metals build-up of greater than about 4 wt. % nickel plus vanadium, a hydrogenation component selected from the group consisting of Group VIB metals and Group VIII metals and is regenerated spent hydroprocessing catalyst regenerated by a process comprising the steps: partially decoking the spent catalyst in an initial coke-burning step; impregnating the partially decoked catalyst with a Group IIA metal-containing impregnation solution; and decoking the impregnated catalyst in a final coke-burning step wherein the impregnated catalyst is contacted with an oxygen-containing gas at a temperature of about 600 degrees F to about 1400 degrees F

Characterization of steam-reforming catalysts

Directory of Open Access Journals (Sweden)

Santos D. C. R.M.

2004-01-01

Full Text Available The effect of the addition of Mg and Ca to Ni/ a-Al2O3 catalysts was investigatedstudied, aiming to detail the promotion mechanismaddress their role as promoters in the steam reforming reaction. Temperature- programmed reduction and H2 and CO temperature-programmed desorption experiments indicated that Mg interacts with the metallic phase. Mg-promoted catalysts showed a greater difficulty for Ni precursors reduction besides different probe molecules (H2 and CO adsorbed states. In the conversion of cyclohexane, Mg inhibited the formation of hydrogenolysis products. Nonetheless, the presence of Ca did not influence the metallic phase.

Sulfur Tolerance of Carbide Catalysts Under Hydrocarbon Reforming Conditions

National Research Council Canada - National Science Library

Thomson, William

2004-01-01

.... These conditions are all related to lowering gas-solid mass transfer rate has also been determined that tedious TPR catalyst synthesis techniques are not necessary to achieve either catalyst activity or stability...

The reformation of liquid hydrocarbons in an aqueous discharge reactor

International Nuclear Information System (INIS)

Zhang, Xuming; Cha, Min Suk

2015-01-01

We present an aqueous discharge reactor for the reformation of liquid hydrocarbons. To increase a dielectric constant of a liquid medium, we added distilled water to iso-octane and n-dodecane. As expected, we found decreased discharge onset voltage and increased discharge power with increased water content. Results using optical emission spectroscopy identified OH radicals and O atoms as the predominant oxidative reactive species with the addition of water. Enriched CH radicals were also visualized, evidencing the existence of cascade carbon–carbon cleavage and dehydrogenation processes in the aqueous discharge. The gaseous product consisted primarily of hydrogen, carbon monoxide, and unsaturated hydrocarbons. The composition of the product was readily adjustable by varying the volume of water added, which demonstrated a significant difference in composition with respect to the tested liquid hydrocarbon. In this study, we found no presence of CO 2 emissions or the contamination of the reactor by solid carbon deposition. These findings offer a new approach to the reforming processes of liquid hydrocarbons and provide a novel concept for the design of a practical and compact plasma reformer. (paper)

Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

Energy Technology Data Exchange (ETDEWEB)

Davidson, Stephen D. [Energy and Environmental; Spies, Kurt A. [Energy and Environmental; Mei, Donghai [Energy and Environmental; Kovarik, Libor [Energy and Environmental; Kutnyakov, Igor [Energy and Environmental; Li, Xiaohong S. [Energy and Environmental; Lebarbier Dagle, Vanessa [Energy and Environmental; Albrecht, Karl O. [Energy and Environmental; Dagle, Robert A. [Energy and Environmental

2017-09-11

We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, and activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.

The reformation of liquid hydrocarbons in an aqueous discharge reactor

KAUST Repository

Zhang, Xuming; Cha, Min

2015-01-01

deposition. These findings offer a new approach to the reforming processes of liquid hydrocarbons and provide a novel concept for the design of a practical and compact plasma reformer. © 2015 IOP Publishing Ltd.

Sintering of nickel steam reforming catalysts

DEFF Research Database (Denmark)

Sehested, Jens; Larsen, Niels Wessel; Falsig, Hanne

2014-01-01

. In this paper, particle migration and coalescence in nickel steam reforming catalysts is studied. Density functional theory calculations indicate that Ni-OH dominate nickel transport at nickel surfaces in the presence of steam and hydrogen as Ni-OH has the lowest combined energies of formation and diffusion...

Review of Heterogeneous Catalysts for Catalytically Upgrading Vegetable Oils into Hydrocarbon Biofuels

Directory of Open Access Journals (Sweden)

Xianhui Zhao

2017-03-01

Full Text Available To address the issues of greenhouse gas emissions associated with fossil fuels, vegetable oilseeds, especially non-food oilseeds, are used as an alternative fuel resource. Vegetable oil derived from these oilseeds can be upgraded into hydrocarbon biofuel. Catalytic cracking and hydroprocessing are two of the most promising pathways for converting vegetable oil to hydrocarbon biofuel. Heterogeneous catalysts play a critical role in those processes. The present review summarizes current progresses and remaining challenges of vegetable oil upgrading to biofuel. The catalyst properties, applications, deactivation, and regeneration are reviewed. A comparison of catalysts used in vegetable oil and bio-oil upgrading is also carried out. Some suggestions for heterogeneous catalysts applied in vegetable oil upgrading to improve the yield and quality of hydrocarbon biofuel are provided for further research in the future.

The Hydrocarbon Pool in Ethanol-to-Gasoline over HZSM-5 Catalysts

DEFF Research Database (Denmark)

Johansson, Roger; Hruby, S.L.; Hansen, Jeppe Rass

2009-01-01

It is shown that the conversion of ethanol-to-gasoline over an HZSM-5 catalyst yields essentially the same product distribution as for methanol-to-gasoline performed over the same catalyst. Interestingly, there is a significant difference between the identity of the hydrocarbon molecules trapped...... inside the HZSM-5 catalyst when ethanol is used as a feed instead of methanol. In particular, the hydrocarbon pool contains a significant amount of ethylsubstituted aromatics when ethanol is used as feedstock, but there remains only methyl-substituted aromatics in the product slate....

Composite catalyst for carbon monoxide and hydrocarbon oxidation

Science.gov (United States)

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Ni Catalysts Supported on Modified Alumina for Diesel Steam Reforming

Directory of Open Access Journals (Sweden)

Antonios Tribalis

2016-01-01

Full Text Available Nickel catalysts are the most popular for steam reforming, however, they have a number of drawbacks, such as high propensity toward coke formation and intolerance to sulfur. In an effort to improve their behavior, a series of Ni-catalysts supported on pure and La-, Ba-, (La+Ba- and Ce-doped γ-alumina has been prepared. The doped supports and the catalysts have been extensively characterized. The catalysts performance was evaluated for steam reforming of n-hexadecane pure or doped with dibenzothiophene as surrogate for sulphur-free or commercial diesel, respectively. The undoped catalyst lost its activity after 1.5 h on stream. Doping of the support with La improved the initial catalyst activity. However, this catalyst was completely deactivated after 2 h on stream. Doping with Ba or La+Ba improved the stability of the catalysts. This improvement is attributed to the increase of the dispersion of the nickel phase, the decrease of the support acidity and the increase of Ni-phase reducibility. The best catalyst of the series doped with La+Ba proved to be sulphur tolerant and stable for more than 160 h on stream. Doping of the support with Ce also improved the catalytic performance of the corresponding catalyst, but more work is needed to explain this behavior.

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

The reformation of liquid hydrocarbons in an aqueous discharge reactor

KAUST Repository

Zhang, Xuming

2015-04-21

We present an aqueous discharge reactor for the reformation of liquid hydrocarbons. To increase a dielectric constant of a liquid medium, we added distilled water to iso-octane and n-dodecane. As expected, we found decreased discharge onset voltage and increased discharge power with increased water content. Results using optical emission spectroscopy identified OH radicals and O atoms as the predominant oxidative reactive species with the addition of water. Enriched CH radicals were also visualized, evidencing the existence of cascade carbon-carbon cleavage and dehydrogenation processes in the aqueous discharge. The gaseous product consisted primarily of hydrogen, carbon monoxide, and unsaturated hydrocarbons. The composition of the product was readily adjustable by varying the volume of water added, which demonstrated a significant difference in composition with respect to the tested liquid hydrocarbon. In this study, we found no presence of CO2 emissions or the contamination of the reactor by solid carbon deposition. These findings offer a new approach to the reforming processes of liquid hydrocarbons and provide a novel concept for the design of a practical and compact plasma reformer. © 2015 IOP Publishing Ltd.

Catalysts for the production of hydrocarbons from carbon monoxide and water

Science.gov (United States)

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

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.

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

Science.gov (United States)

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

2013-01-16

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

Steam reforming of bio-ethanol over Ni on Ce-ZrO2 support: Influence of redox properties on the catalyst reactivity

Directory of Open Access Journals (Sweden)

Sumittra Charojrochkul

2006-11-01

Full Text Available The steam reforming of ethanol over Ni on Ce-ZrO2 support, (Ni/ Ce-ZrO2 were studied. The catalyst provides significantly higher reforming reactivity and excellent resistance toward carbon deposition compared to Ni/Al2O3 under the same conditions. At the temperature above 800ºC, the main products from the reforming processes over Ni/Ce-ZrO2 were H2, CO, and CO2 with small amount of CH4 depending on the inlet ethanol/steam and oxygen/ethanol ratios, whereas high hydrocarbon compounds i.e., C2H4 and C2H6 were also observed from the reforming of ethanol over Ni/Al2O3 in the range of conditions studied (700- 1000ºC.These excellent ethanol reforming performances of Ni/Ce-ZrO2 in terms of stability, reactivity and product selectivities are due to the high redox property of Ce-ZrO2. During the ethanol reforming process, in addition to the reactions on Ni surface, the gas-solid reactions between the gaseous components presented in the system (C2H5OH, C2H6, C2H4, CH4, CO2, CO, H2O, and H2 and the lattice oxygen (Ox on Ce-ZrO2 surface also take place. Among these redox reactions, the reactions of adsorbed surface hydrocarbons with the lattice oxygen (Ox (CnHm + Ox → nCO + m/2(H2 + Ox-n can eliminate the formation of high hydrocarbons (C2H6 and C2H4, which easily decompose and form carbon species on Ni surface (CnHm→ nC + m/2H2.

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

Directory of Open Access Journals (Sweden)

Kah Weng Siew

2013-12-01

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

Methanol conversion to hydrocarbons using modified clinoptilolite catalysts. Investigation of catalyst lifetime and reactivation

Energy Technology Data Exchange (ETDEWEB)

Hutchings, G J; Themistocleous, T; Copperthwaite, R G

1988-10-17

A study of the deactivation and reactivation of modified clinoptilolite catalysts for methanol conversion to hydrocarbons is reported. Clinoptilolite catalysts, modified by either ammonium ion exchange or hydrochloric acid treatment, exhibit a short useful catalyst lifetime for this reaction (ca. 2-3 h) due to a high rate of coke deposition (3-5.10/sup -3/ g carbon/g catalyst/h). A comparative study of reactivation using oxygen, nitrous oxide and ozone/oxygen as oxidants indicated that nitrous oxide reactivation gives improved catalytic performance when compared to the activity and lifetime of the fresh catalyst. Both oxygen and ozone/oxygen were found to be ineffective for the reactivation of clinoptilolite. Initial studies of in situ on-line reactivation are also described. 3 figs., 15 refs., 4 tabs.

Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

Science.gov (United States)

Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

2018-09-01

The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

Reforming petroleum-based fuels for fuel cell vehicles : composition-performance relationships

International Nuclear Information System (INIS)

Kopasz, J. P.; Miller, L. E.; Ahmed, S.; Devlin, P. R.; Pacheco, M.

2001-01-01

Onboard reforming of petroleum-based fuels, such as gasoline, may help ease the introduction of fuel cell vehicles to the marketplace. Although gasoline can be reformed, it is optimized to meet the demands of ICEs. This optimization includes blending to increase the octane number and addition of oxygenates and detergents to control emissions. The requirements for a fuel for onboard reforming to hydrogen are quite different than those for combustion. Factors such as octane number and flame speed are not important; however, factors such as hydrogen density, catalyst-fuel interactions, and possible catalyst poisoning become paramount. In order to identify what factors are important in a hydrocarbon fuel for reforming to hydrogen and what factors are detrimental, we have begun a program to test various components of gasoline and blends of components under autothermal reforming conditions. The results indicate that fuel composition can have a large effect on reforming behavior. Components which may be beneficial for ICEs for their octane enhancing value were detrimental to reforming. Fuels with high aromatic and naphthenic content were more difficult to reform. Aromatics were also found to have an impact on the kinetics for reforming of paraffins. The effects of sulfur impurities were dependent on the catalyst. Sulfur was detrimental for Ni, Co, and Ru catalysts. Sulfur was beneficial for reforming with Pt catalysts, however, the effect was dependent on the sulfur concentration

Hydrogen production via reforming of biogas over nanostructured Ni/Y catalyst: Effect of ultrasound irradiation and Ni-content on catalyst properties and performance

Energy Technology Data Exchange (ETDEWEB)

Sharifi, Mahdi [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Abdollahifar, Mozaffar [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of)

2014-12-15

Highlights: • Synthesis of nanostructured Ni/Y catalyst by sonochemical and impregnation methods. • Enhancement of size distribution and active phase dispersion by employing sonochemical method. • Evaluation of biogas reforming over Ni/Y catalyst with different Ni-loadings. • Preparation of highly active and stable catalyst with low Ni content for biogas reforming. • Getting H{sub 2}/CO very close to equilibrium ratio by employing sonochemical method. - Abstract: The effect of ultrasound irradiation and various Ni-loadings on dispersion of active phase over zeolite Y were evaluated in biogas reforming for hydrogen production. X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray, Brunauer–Emmett–Teller, Fourier transform infrared analysis and TEM analysis were employed to observe the characteristics of nanostructured catalysts. The characterizations implied that utilization of ultrasound irradiation enhanced catalyst physicochemical properties including high dispersion of Ni on support, smallest particles size and high catalyst surface area. The reforming reactions were carried out at GHSV = 24 l/g.h, P = 1 atm, CH{sub 4}/CO{sub 2} = 1 and temperature range of 550–850 °C. Activity test displayed that ultrasound irradiated Ni(5 wt.%)/Y had the best performance and the activity remained stable during 600 min. Furthermore, the proposed reaction mechanism showed that there are three major reaction channels in biogas reforming.

Multiphase catalysts for selective reduction of NOx with hydrocarbons

International Nuclear Information System (INIS)

Maisuls, S.E.

2000-01-01

Among the existing proposed solutions to reduce emission of NOx there is a promising alternative, the so-called (HC-SCR) selective catalytic reduction of NOx using hydrocarbons as reductant. This thesis is part of a worldwide effort devoted to gain knowledge on the selective catalytic reduction of NOx with hydrocarbons with the final goal to contribute to the development of suitable catalysts for the above mentioned process. Chapter 2 describes the details of the experimental set-up and of the analytical methods employed. Among the catalyst for HC-SCR, Co-based catalyst are known to be active and selective, thus, a study on a series of Co-based catalysts, supported on zeolites, was undertaken and the results are presented in Chapter 3. Correlation between catalytic characteristics and kinetic results are employed to understand the working catalyst and this is used as a basis for catalyst optimization. With the intention to prepare a multi-functional catalyst that will preserve the desired characteristics of the individual components, minimizing their negative aspects, catalysts based on Co-Pt, supported on ZSM-5, were investigated. In Chapter 4 the results of this study are discussed. A bimetallic Co-Pt/ZSM-5 catalysts with low Pt contents (0.1 wt %) showed a synergistic effect by combining high stability and activity of Pt catalysts with the high N2 selectivity of Co catalysts. Furthermore, it was found to be sulfur- and water-tolerant. Its positive qualities brought us to study the mechanism that takes place over this catalyst during HC-SCR. The results of an in-situ i.r mechanistic study over this catalyst is reported in Chapter 5. From the results presented in Chapter 5 a mechanism operating over the Co-Pt/ZSM-5 catalyst is proposed. The modification of Co catalyst with Pt improved the catalysts. However, further improvement was found to be hindered by high selectivity to N2O. Since Rh catalysts are generally less selective to N2O, the modification of Co

Method of treating emissions of a hybrid vehicle with a hydrocarbon absorber and a catalyst bypass system

Science.gov (United States)

Roos, Bryan Nathaniel; Gonze, Eugene V; Santoso, Halim G; Spohn, Brian L

2014-01-14

A method of treating emissions from an internal combustion engine of a hybrid vehicle includes directing a flow of air created by the internal combustion engine when the internal combustion engine is spinning but not being fueled through a hydrocarbon absorber to collect hydrocarbons within the flow of air. When the hydrocarbon absorber is full and unable to collect additional hydrocarbons, the flow of air is directed through an electrically heated catalyst to treat the flow of air and remove the hydrocarbons. When the hydrocarbon absorber is not full and able to collect additional hydrocarbons, the flow of air is directed through a bypass path that bypasses the electrically heated catalyst to conserve the thermal energy stored within the electrically heated catalyst.

Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

Science.gov (United States)

Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

2015-12-01

The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

Methane Steam Reforming Kinetics for a Rhodium-Based Catalyst

DEFF Research Database (Denmark)

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

2010-01-01

Methane steam reforming is the key reaction to produce synthesis gas and hydrogen at the industrial scale. Here the kinetics of methane steam reforming over a rhodium-based catalyst is investigated in the temperature range 500-800 A degrees C and as a function of CH4, H2O and H-2 partial pressures....... The methane steam reforming reaction cannot be modeled without taking CO and H coverages into account. This is especially important at low temperatures and higher partial pressures of CO and H-2. For methane CO2 reforming experiments, it is also necessary to consider the repulsive interaction of CO...

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  |  

Non-catalytic recuperative reformer

Science.gov (United States)

Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

2015-12-22

A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

Radiant non-catalytic recuperative reformer

Energy Technology Data Exchange (ETDEWEB)

Khinkis, Mark J.; Kozlov, Aleksandr P.

2017-10-31

A radiant, non-catalytic recuperative reformer has a flue gas flow path for conducting hot exhaust gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is positioned adjacent to the flue gas flow path to permit heat transfer from the hot exhaust gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, a portion of the reforming mixture flow path is positioned outside of flue gas flow path for a relatively large residence time.

Steam reforming and oxidative steam reforming of methanol over CuO-CeO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Udani, P.P.C.; Gunawardana, P.V.D.S.; Lee, Hyun Chan; Kim, Dong Hyun [Department of Chemical Engineering, Kyungpook National University, Daegu 702-701 (Korea)

2009-09-15

Steam reforming (SRM) and oxidative steam reforming of methanol (OSRM) were carried out over a series of coprecipitated CuO-CeO{sub 2} catalysts with varying copper content in the range of 30-80 at.% Cu (= 100 x Cu/(Cu + Ce)). The effects of copper content, reaction temperature and O{sub 2} concentration on catalytic activity were investigated. The activity of CuO-CeO{sub 2} catalysts for SRM and OSRM increased with the copper content and 70 at.% CuO-CeO{sub 2} catalyst showed the highest activity in the temperature range of 160-300 C for both SRM and OSRM. After SRM or OSRM, the copper species in the catalysts observed by XRD were mainly metallic copper with small amount of CuO and Cu{sub 2}O, an indication that metallic copper is an active species in the catalysis of both SRM and OSRM. It was observed that the methanol conversion increased considerably with the addition of O{sub 2} into the feed stream, indicating that the partial oxidation of methanol (POM) is much faster than SRM. The optimum 70 at.% CuO-CeO{sub 2} catalyst showed stable activities for both SRM and OSRM reactions at 300 C. (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.

CATALYTIC STEAM REFORMING OF CHLOROCARBONS: CATALYST COMPARISONS. (R826694C633)

Science.gov (United States)

Catalyst candidates for steam reforming chlorocarbons have been screened for activity using methyl chloride as a model reactant. At 500°C, a H2O/C ratio of about 10 and a GHSV of 254 000 h-1, catalysts comprising 0.5% loading of the metals ...

Preparation and characterization of the perovskite catalysts : activity studies for diesel surrogate (dodecane) reforming

Energy Technology Data Exchange (ETDEWEB)

Kondakindi, R.; Kundu, A.; Karan, K.; Peppley, B. [Queen' s-RMC Fuel Cell Research Centre, Kingston, ON (Canada)

2009-07-01

Canada's northern communities rely on diesel fuel for generating electricity. The process of converting diesel to electricity in internal combustion engines is not efficient and generates significant amounts of unwanted products. This paper presented an alternative process whereby diesel is reformed into hydrogen-rich reformate which can then be fed to a solid oxide fuel cell. This alternative process converts energy more efficiently and eliminates the formation of nitrogen oxides (NOx) and soot. This study focused on the development of LaFeO{sub 3} based perovskite catalysts for diesel reforming. The activity of the perovskite catalysts was assessed for steam reforming of dodecane, a surrogate for diesel. In order to study the effect on catalytic activity, various perovskite materials were prepared by doping the perovskite at A-site to minimize the coke deposition and at B-site to improve the activity. Preliminary results for dodecane reforming for selected perovskites were promising. Additional testing is underway regarding catalyst activity and stability studies as well carbon and sulphur poisoning.

Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

Science.gov (United States)

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-12-25

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

CATALYTIC STEAM REFORMING OF CHLOROCARBONS: CATALYST COMPARISONS. (R822721C633)

Science.gov (United States)

Catalyst candidates for steam reforming chlorocarbons have been screened for activity using methyl chloride as a model reactant. At 500°C, a H2O/C ratio of about 10 and a GHSV of 254 000 h-1, catalysts comprising 0.5% loading of the metals o...

Hydrogen-rich gas production from waste plastics by pyrolysis and low-temperature steam reforming over a ruthenium catalyst

International Nuclear Information System (INIS)

Namioka, Tomoaki; Saito, Atsushi; Inoue, Yukiharu; Park, Yeongsu; Min, Tai-jin; Roh, Seon-ah; Yoshikawa, Kunio

2011-01-01

Operating conditions for low-temperature pyrolysis and steam reforming of plastics over a ruthenium catalyst were investigated. In the range studied, the highest gas and lowest coke fractions for polystyrene (PS) with a 60 g h -1 scale, continuous-feed, two-stage gasifier were obtained with a pyrolyzer temperature of 673 K, steam reforming temperature of 903 K, and weight hourly space velocity (WHSV) of 0.10 g-sample g-catalyst -1 h -1 . These operating conditions are consistent with optimum conditions reported previously for polypropylene. Our results indicate that at around 903 K, the activity of the ruthenium catalyst was high enough to minimize the difference between the rates of the steam reforming reactions of the pyrolysates from polystyrene and polypropylene. The proposed system thus has the flexibility to compensate for differences in chemical structures of municipal waste plastics. In addition, the steam reforming temperature was about 200 K lower than the temperature used in a conventional Ni-catalyzed process for the production of hydrogen. Low-temperature steam reforming allows for lower thermal input to the steam reformer, which results in an increase in thermal efficiency in the proposed process employing a Ru catalyst. Because low-temperature steam reforming can be also expected to reduce thermal degradation rates of the catalyst, the pyrolysis-steam reforming process with a Ru catalyst has the potential for use in small-scale production of hydrogen-rich gas from waste plastics that can be used for power generation.

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.

Design of a surface alloy catalyst for steam reforming

DEFF Research Database (Denmark)

Besenbacher, F.; Chorkendorff, Ib; Clausen, B.S.

1998-01-01

Detailed studies of elementary chemical processes on well-characterized single crystal surfaces have contributed substantially to the understanding of heterogeneous catalysis. insight into the structure of surface alloys combined with an understanding of the relation between the surface compositi...... and reactivity is shown to lead directly to new ideas for catalyst design, The feasibility of such an approach is illustrated by the synthesis, characterization, and tests of a high-surface area gold-nickel catalyst for steam reforming....

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.

Two-step processing of oil shale to linear hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Eliseev, O.L.; Ryzhov, A.N.; Latypova, D.Zh.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry; Avakyan, T.A. [Gubkin Russian State University of Oil and Gas, Moscow (Russian Federation)

2013-11-01

Thermal and catalytic steam reforming of oil shale mined from Leningrad and Kashpir deposits was studied. Experiments were performed in fixed bed reactor by varying temperature and steam flow rate. Data obtained were approximated by empirical formulas containing some parameters calculated by least-squares method. Thus predicting amount of hydrogen, carbon monoxide and methane in producer gas is possible for given particular kind of oil shale, temperature and steam flow rate. Adding Ni catalyst enriches hydrogen and depletes CO content in effluent gas at low gasification temperatures. Modeling gas simulating steam reforming gases (H{sub 2}, CO, CO{sub 2}, and N{sub 2} mixture) was tested in hydrocarbon synthesis over Co-containing supported catalyst. Selectivity of CO conversion into C{sub 5+} hydrocarbons reaches 84% while selectivity to methane is 7%. Molecular weight distribution of synthesized alkanes obeys Anderson-Schulz-Flory equation and chain growth probability 0.84. (orig.)

Catalytic reforming of glycerol in supercritical water over bimetallic Pt-Ni catalyst

NARCIS (Netherlands)

Chakinala, A.G.; van Swaaij, Willibrordus Petrus Maria; Kersten, Sascha R.A.; de Vlieger, Dennis; Seshan, Kulathuiyer; Brilman, Derk Willem Frederik

2013-01-01

Catalytic reforming of pure glycerol for the production of hydrogen at low temperature and short residence times in supercritical water was investigated using a bimetallic Pt–Ni catalyst supported on alumina. Initial tests were carried out to study the reforming activity of bimetallic Pt–Ni

Steam reforming of bio-oil from coconut shell pyrolysis over Fe/olivine catalyst

International Nuclear Information System (INIS)

Quan, Cui; Xu, Shaoping; Zhou, Congcong

2017-01-01

Highlights: • Steam reforming of the actual bio-oil was investigated with Fe/olivine catalyst. • Most of phenols in bio-oil were converted into gas products. • A carbon conversion of 97.2% was obtained under optimized conditions. - Abstract: Catalytic steam reforming of coconut shell pyrolysis bio-oil over Fe/olivine catalyst was conducted in a fixed-bed quartz reactor. The effects of calcination temperature, iron loading, reaction temperature, steam to carbon ratio (S/C), bio-oil weight hourly space velocity (W b HSV) on gas composition and carbon conversion were investigated. The results indicate that Fe/olivine has good activity for steam reforming of bio-oil, the couple Fe 2+/3+ /Fe 2+ may be sufficiently efficient for C–C, C–O and C–H breaking. After steam reforming, most of the phenolics in pyrolysis oil are converted into light molecular compounds such as H 2 , CO, CO 2 , and CH 4 . The H 2 concentration and carbon conversion were enhanced by increasing reaction temperature from 750 to 800 °C and the S/C from 1.5 to 2, but decreased with increasing calcination temperature. In the W b HSV range of 0.5–0.6, the hydrogen concentration decreased obviously, whereas it decreased slightly by further increasing W b HSV. The highest hydrogen concentration of 47.6 vol% was obtained among the catalysts tested, and the best carbon conversion was 97.2% over 10% Fe/olivine catalyst under the reforming conditions of temperature = 800 °C, W b HSV = 0.5, S/C = 2.

Preparation and characterization of nickel catalysts supported on cerium for obtaining hydrogen from steam reforming of ethanol

International Nuclear Information System (INIS)

Urbaninho, A.B.; Bergamaschi, V.S.; Ferreira, J.C.

2016-01-01

The Ni/Ce catalysts for were prepared by co- precipitation method with a view to their use in steam reforming of ethanol to produce a hydrogen-rich gas mixture. The catalysts were characterized by scanning electron microscopy; x-ray dispersive Spectroscopy and surface area BET method. This paper proposes to prepare, characterize and test nickel catalyst supported on cerium in order to obtain a material with higher activity and selectivity of the catalyst using the steam reforming reaction of ethanol, by varying the reaction temperature, molar ratio water/ethanol and uptime. The catalytic tests were monitored by chemical analysis of syngas from steam reforming of ethanol using an analysis online by gas Chromatograph in the reactor. (author)

Solar central receiver reformer system for ammonia plants

Science.gov (United States)

1980-07-01

An overview of a study to retrofit the Valley Nitrogen Producers, Inc., El Centro, California 600 ST/SD Ammonia Plant with Solar Central Receiver Technology is presented. The retrofit system consists of a solar central receiver reformer (SCRR) operating in parallel with the existing fossil fired reformer. Steam and hydrocarbon react in the catalyst filled tubes of the inner cavity receiver to form a hydrogen rich mixture which is the syngas feed for the ammonia production. The SCRR system will displace natural gas presently used in the fossil reformer combustion chamber.

Determination of catalyst residues in hydrocarbon fuels by instrumental neutron activation analysis

International Nuclear Information System (INIS)

Burgess, D.D.

1982-01-01

A procedure has been developed for the determination of entrained catalytic cracking catalyst in hydrocarbon fuels. Aluminium is measured by instrumental neutron activation analysis and the amount of catalyst present is calculated from the amount of aluminium found and the known composition of the catalyst. Entrained catalyst may be determined at levels above 3 ppm with a precision of +-2%-25% according to sample composition. Only simple procedures are required. Vanadium may reduce sensitivity by dead time and pulse pile-up. No other interferences were observed. (author)

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.

Aqueous phase reforming of ethylene glycol - Role of intermediates in catalyst performance

NARCIS (Netherlands)

de Vlieger, Dennis; Mojet, Barbara; Lefferts, Leonardus; Seshan, Kulathuiyer

2012-01-01

Liquid product formation during the aqueous catalytic reforming of ethylene glycol (EG) was studied up to 450 °C and 250 bar pressure. Methanol, ethanol, and acetic acid were the main liquid by-products during EG reforming in the presence of alumina-supported Pt and Pt–Ni catalysts. The effect of

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)

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 ...

Catalyst Deactivation and Regeneration in Low Temperature Ethanol Steam Reforming with Rh/CeO2-ZrO2 Catalysts

Energy Technology Data Exchange (ETDEWEB)

Roh, Hyun-Seog; Platon, Alex; Wang, Yong; King, David L.

2006-08-01

Rh/CeO2-ZrO2 catalysts with various CeO2/ZrO2 ratios have been applied to H2 production from ethanol steam reforming at low temperatures. The catalysts all deactivated with time on stream (TOS) at 350 C. The addition of 0.5% K has a beneficial effect on catalyst stability, while 5% K has a negative effect on catalytic activity. The catalyst could be regenerated considerably even at ambient temperature and could recover its initial activity after regeneration above 200 C with 1% O2. The results are most consistent with catalyst deactivation due to carbonaceous deposition on the catalyst.

High aspect ratio catalytic reactor and catalyst inserts therefor

Science.gov (United States)

Lin, Jiefeng; Kelly, Sean M.

2018-04-10

The present invention relates to high efficient tubular catalytic steam reforming reactor configured from about 0.2 inch to about 2 inch inside diameter high temperature metal alloy tube or pipe and loaded with a plurality of rolled catalyst inserts comprising metallic monoliths. The catalyst insert substrate is formed from a single metal foil without a central supporting structure in the form of a spiral monolith. The single metal foil is treated to have 3-dimensional surface features that provide mechanical support and establish open gas channels between each of the rolled layers. This unique geometry accelerates gas mixing and heat transfer and provides a high catalytic active surface area. The small diameter, high aspect ratio tubular catalytic steam reforming reactors loaded with rolled catalyst inserts can be arranged in a multi-pass non-vertical parallel configuration thermally coupled with a heat source to carry out steam reforming of hydrocarbon-containing feeds. The rolled catalyst inserts are self-supported on the reactor wall and enable efficient heat transfer from the reactor wall to the reactor interior, and lower pressure drop than known particulate catalysts. The heat source can be oxygen transport membrane reactors.

Precious metal assay analysis of fresh reforming catalyst by x-ray fluorescence spectrometry

International Nuclear Information System (INIS)

McElroy, F.C.; Mulhall, J.M.

1991-01-01

This paper reports that precious metal analysis of fresh reforming catalysts are typically performed by both the catalyst manufacturer and buyer to arrive at a financial settlement on the quantity of metal in each lot of commercial catalyst. Traditional assay methods involve a variety of fire assay or wet chemical acid digestion schemes coupled with gravimetric, colorimetic, or titrimetric measurement for precious metals. Methods must have sufficient precision and accuracy to afford interlaboratory agreement of within one half of one percent relative between the catalyst supplier and purchaser. To meet this requirement many laboratories rely on classical methods. Unfortunately these proceeders are labor intensive and time consuming. X-ray fluorescence has the inherent instrument precision to achieve typical intralaboratory precision of 0.5% RSD on a wide variety of elements and numerous sample types. We have developed an X-ray fluorescence method for the assay quality analysis of fresh reforming catalyst containing platinum, rhenium, and iridium. This method was applied to numerous samples over the past five years

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

Science.gov (United States)

Cavendish, Rio

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

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

Energy Technology Data Exchange (ETDEWEB)

Rodin, J.

2010-07-15

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

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.

Hydrogen Production by Steam Reforming of Natural Gas Over Vanadium-Nickel-Alumina Catalysts.

Science.gov (United States)

Yoo, Jaekyeong; Park, Seungwon; Song, Ji Hwan; Song, In Kyu

2018-09-01

A series of vanadium-nickel-alumina (xVNA) catalysts were prepared by a single-step sol-gel method with a variation of vanadium content (x, wt%) for use in the hydrogen production by steam reforming of natural gas. The effect of vanadium content on the physicochemical properties and catalytic activities of xVNA catalysts in the steam reforming of natural gas was investigated. It was found that natural gas conversion and hydrogen yield showed volcano-shaped trends with respect to vanadium content. It was also revealed that natural gas conversion and hydrogen yield increased with decreasing nickel crystallite size.

Bio-inspired Iron Catalysts for Hydrocarbon Oxidations

Energy Technology Data Exchange (ETDEWEB)

Que, Jr., Lawrence [Univ. of Minnesota, Minneapolis, MN (United States)

2016-03-22

Stereoselective oxidation of C–H and C=C bonds are catalyzed by nonheme iron enzymes. Inspired by these bioinorganic systems, our group has been exploring the use of nonheme iron complexes as catalysts for the oxidation of hydrocarbons using H2O2 as an environmentally friendly and atom-efficient oxidant in order to gain mechanistic insights into these novel transformations. In particular, we have focused on clarifying the nature of the high-valent iron oxidants likely to be involved in these transformations.

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.

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)

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.

Study of Catalyst Variation Effect in Glycerol Conversion Process to Hydrogen Gas by Steam Reforming

Science.gov (United States)

Widayat; Hartono, R.; Elizabeth, E.; Annisa, A. N.

2018-04-01

Along with the economic development, needs of energy being increase too. Hydrogen as alternative energy has many usages. Besides that, hydrogen is one source of energy that is a clean fuel, but process production of hydrogen from natural gas as a raw material has been used for a long time. Therefore, there is need new invention to produce hydrogen from the others raw material. Glycerol, a byproduct of biodiesel production, is a compound which can be used as a raw material for hydrogen production. By using glycerol as a raw material of hydrogen production, we can get added value of glycerol as well as an energy source solution. The process production of hydrogen by steam reforming is a thermochemical process with efficiency 70%. This process needs contribution of catalyst to improve its efficiency and selectivity of the process. In this study will be examined the effect variation of catalyst for glycerol conversion process to hydrogen by steam reforming. The method for catalyst preparation was variation of catalyst impregnation composition, catalyst calcined with difference concentration of hydrochloric acid and calcined with difference hydrochloric acid ratio. After that, all of catalyst which have been prepared, used for steam reforming process for hydrogen production from glycerol as a raw material. From the study, the highest yield of hydrogen gas showed in the process production by natural zeolite catalyst with 1:15 Hydrochloric acid ratio was 42.28%. Hydrogen yield for 2M calcined natural zeolite catalyst was 38.37%, for ZSM-5 catalyst was 15.83%, for 0.5M calcined natural zeolite was 13.09% and for ultrasonic natural zeolite was 11.43%. The lowest yield of hydrogen gas showed in catalyst 2Zn/ZSM-5 with 11.22%. This result showed that hydrogen yield product was affected by catalyst variation because of the catalyst has difference characteristic and difference catalytic activity after the catalyst preparation process.

Zircon Supported Copper Catalysts for the Steam Reforming of Methanol

Science.gov (United States)

Widiastri, M.; Fendy, Marsih, I. N.

2008-03-01

Steam reforming of methanol (SRM) is known as one of the most favorable catalytic processes for producing hydrogen. Current research on zirconia, ZrO2 supported copper catalyst revealed that CuO/ZrO2 as an active catalyst for the SRM. Zircon, ZrSiO4 is available from the by-product of tin mining. In the work presented here, the catalytic properties of CuO/ZrSiO4 with various copper oxide compositions ranging from 2.70% (catalyst I), 4.12% (catalyst II), and 7.12%-mass (catalyst III), synthesized by an incipient wetness impregnation technique, were investigated to methanol conversion, selectivity towards CO formation, and effect of ZnO addition (7.83%CuO/8.01%ZnO/ZrSiO4 = catalyst V). The catalytic activity was obtained using a fixed bed reactor and the zircon supported catalyst activity was compared to those of CuO/ZnO/Al2O3 catalyst (catalyst IV) and commercial Kujang LTSC catalyst. An X-ray powder diffraction (XRD) analysis was done to identify the abundant phases of the catalysts. The catalysts topography and particle diameter were measured with scanning electron microscopy (SEM) and composition of the catalysts was measured by SEM-EDX, scanning electron microscope-energy dispersive using X-ray analysis. The results of this research provide information on the possibility of using zircon (ZrSiO4) as solid support for SRM catalysts.

Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

Directory of Open Access Journals (Sweden)

Ting Ma

2014-04-01

Full Text Available The conversion of syngas (CO + H2 to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent. Methanol was synthesized from syngas over Cu-ZnO; subsequently, was converted to hydrocarbons through the formation of dimethyl ether (DME over the metal-loaded ZSM-5. When 0.5 wt% Pd/ZSM-5 and 5 wt% Cu/ZSM-5 among the metal-loaded ZSM-5 catalysts with Pd, Co, Fe or Cu were employed as a portion of the hybrid catalyst, the gasoline-ranged hydrocarbons were selectively produced (the gasoline-ranged hydrocarbons in all hydrocarbons: 59% for the hybrid catalyst with Pd/ZSM-5 and 64% for that with Cu/ZSM-5 with a similar CO conversion during the reaction. An increase in the Cu loading on ZSM-5 resulted in increasing the yield of the gasoline-ranged hydrocarbons, and in decreasing the yield of DME. Furthermore, the hybrid catalyst with Cu/ZSM-5 exhibited no deactivation for 30 h of the reaction. It was revealed that a hybrid catalyst containing Cu/ZSM-5 was efficient in the selective synthesis of gasoline-ranged hydrocarbons from syngas via methanol in the near-critical n-hexane fluid.

Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

Science.gov (United States)

Dade, William N.

Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

Plasma steam reforming of E85 for hydrogen rich gas production

International Nuclear Information System (INIS)

Zhu Xinli; Hoang Trung; Lobban, Lance L; Mallinson, Richard G

2011-01-01

E85 (85 vol% ethanol and 15 vol% gasoline) is a partly renewable fuel that is increasing in supply availability. Hydrogen production from E85 for fuel cell or internal combustion engine applications is a potential method for reducing CO 2 emissions. Steam reforming of E85 using a nonthermal plasma (pulse corona discharge) reactor has been exploited at low temperature (200-300 0 C) without external heating, diluent gas, oxidant or catalyst in this work. Several operational parameters, including the discharge current, E85 concentration and feed flow rate, have been investigated. The results show that hydrogen rich gases (63-67% H 2 and 22-29% CO, with small amounts of CO 2 , C 2 hydrocarbons and CH 4 ) can be produced by this method. A comparison with ethanol reforming and gasoline reforming under identical conditions has also been made and the behaviour of E85 reforming is found to be close to that of ethanol reforming with slightly higher C 2 hydrocarbons yields.

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.

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)

Steam reforming of ethanol over nickel-tungsten catalyst

Energy Technology Data Exchange (ETDEWEB)

Hernandez, I.P.; Fernandez, A.M. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Privada Xochicalco S/N, Temixco, Morelos (Mexico); Gochi-Ponce, Y. [Instituto Tecnologico de Oaxaca, Division de Estudios de Posgrado e Investigacion, Ave. Ing. Victor Bravo Ahuja, esq. Ave. Tecnologico No. 120, Col. Centro. Oaxaca, Oax (Mexico); Contreras Larios, J.L. [Universidad Autonoma Metropolitana Azcapotzalco, CBI., Energia, Av. Sn. Pablo 180, Col. Reynosa, C.P. 02200, Mexico D.F (Mexico)

2010-11-15

Ni-W/Al{sub 2}O{sub 3} catalysts were synthesized, characterized and tested for the steam reforming of ethanol from 300 to 600 C. Addition of Ni and W on the alumina, decreased the surface area and increased the pore volume of the mesoporous materials synthesized. The reaction products obtained were: H{sub 2}, CO{sub 2}, C{sub 2}H{sub 4}, CH{sub 4}, CO{sub 2}, CO and CH{sub 3}CHO. A promoting effect of Ni-W was observed in the conversion of ethanol to H{sub 2} from 15 to 30 wt.% Ni and 1 wt.% W. The selectivity to H{sub 2} on the alumina with Ni-W, was between 66.53 and 68.53% at 550 C, appearing some undesirable products, with low ratio of CO/CO{sub 2}. Reaction was studied on a fixed bed reactor at atmospheric pressure with an ethanol/water molar ratio of 1:4, from 300 to 600 C. The catalysts were characterized by the thermal gravimetric analysis (TGA)-Differential thermal analysis (DTA), N{sub 2} physisorption (BET and BJH methods), X-ray diffraction (XRD) and scanning electron microscopy (SEM), these techniques were used for characterization, before and after of the steam reforming. (author)

One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

Science.gov (United States)

Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

2014-02-21

In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

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.

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.

Development of GREET Catalyst Module

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division

2014-09-01

Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.

Review of Heterogeneous Catalysts for Catalytically Upgrading Vegetable Oils into Hydrocarbon Biofuels

OpenAIRE

Xianhui Zhao; Lin Wei; Shouyun Cheng; James Julson

2017-01-01

To address the issues of greenhouse gas emissions associated with fossil fuels, vegetable oilseeds, especially non-food oilseeds, are used as an alternative fuel resource. Vegetable oil derived from these oilseeds can be upgraded into hydrocarbon biofuel. Catalytic cracking and hydroprocessing are two of the most promising pathways for converting vegetable oil to hydrocarbon biofuel. Heterogeneous catalysts play a critical role in those processes. The present review summarizes current progres...

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

A review of catalytic aqueous-phase reforming of oxygenated hydrocarbons derived from biorefinery water fractions

NARCIS (Netherlands)

Coronado, I.; Stekrova, M.; Reinikainen, M.; Simell, P.; Lefferts, Leonardus; Lehtonen, J.

2016-01-01

Aqueous-phase reforming (APR) of oxygenated hydrocarbons is a process for the production of hydrogen and light alkanes. The reactants of APR remain in liquid phase during the reaction avoiding an energetically demanding vaporization-step compared to processes such as steam reforming (SR).

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.

PREPARATION, CHARACTERIZATION AND CATALYTIC ACTIVITY TEST OF CoMo/ZnO CATALYST ON ETHANOL CONVERSION USING STEAM REFORMING METHOD

Directory of Open Access Journals (Sweden)

Wega Trisunaryanti

2010-06-01

Full Text Available Preparation, characterization and catalytic activity test of CoMo/ZnO catalyst for steam reforming of ethanol have been investigated. The catalysts preparation was carried out by impregnation of Co and/or Mo onto ZnO sample. Water excess was used in ethanol feed for steam reforming process under mol ratio of ethanol:water (1:10. Characterizations of catalysts were conducted by analysis of metal content using Atomic Absorption Spectroscopy (AAS. Determination of catalysts acidity was conducted by gravimetric method of adsorption of pyridine base. Catalytic activity test on ethanol conversion using steam reforming method was conducted in a semi-flow reactor system, at a temperature of 400 oC, for 1.5 h under N2 flow rate of 10 mL/min. Gas product was analyzed by gas chromatograph with TCD system. The results of catalysts characterizations showed that the impregnation of Co and/or Mo metals on ZnO sample increased its acidity and specific surface area. The content of Co in Co/ZnO and CoMo/ZnO catalysts was 1.14 and 0.49 wt%. The Mo content in CoMo/ZnO catalyst was 0.36 wt%. The catalytic activity test result on ethanol conversion showed that the ZnO, Co/ZnO, and CoMo/ZnO catalysts produced gas fraction of 16.73, 28.53, and 35.53 wt%, respectively. The coke production of ZnO, Co/ZnO, and CoMo/ZnO catalysts was 0.86, 0.24, and 0.08 wt%, respectively. The gas products consisted mainly of hydrogen.   Keywords: CoMo/ZnO catalyst, steam reforming, ethanol

Development of Hydrogen Separation Module with Structured Catalyst for Use in Membrane Reformer

International Nuclear Information System (INIS)

Isamu Yasuda; Tatsuya Tsuneki; Yoshinori Shirasaki; Toru Shimamori; Hidekazu Shigaki; Hiroyuki Tanaka

2006-01-01

A new type of hydrogen separation module for use in a membrane reformer was proposed and developed. The new module, what we call MOC (Membrane On Catalyst), was designed to have a membrane of palladium-based alloy prepared on the surface of the tubular structured catalyst that has catalytic activity for steam reforming reaction, thermal expansion matching with the membrane material, proper porosity, mechanical strength and thermal conductivity. The best composition of the structured catalyst was identified in the composites of metallic Ni and YSZ (Yttria-Stabilized Zirconia). A hydrogen separation module was manufactured by electroless plating of Pd with thickness of 7 to 15 microns on the surface of porous sintered tube of Ni-YSZ with an approximate size of 9 mm in diameter and 100 mm in length. The hydrogen permeability measurements have shown hydrogen flux of 25 to 35 cc/min at 550 to 600 C, which is higher than the permeability of the conventional modules using rolled Pd film. (authors)

Experimental comparison among hydrocarbon and oxygenated compounds for their elimination by three-way automotive catalysts

International Nuclear Information System (INIS)

Bart, J.M.; Prigent, M.F.

1992-01-01

Many hydrocarbon species are present in automotive exhaust gases, and three-way Pt-Rh catalysts are commonly used for their elimination. However, most published work on individual hydrocarbon conversion concerns their oxidation in simulated exhaust gases with excess oxygen. This paper reports that this study was therefore undertaken to determine the reactivity of saturated alkanes, olefins, acetylene, aromatics, alcohols or various other oxygenated compounds in steady state conditions with synthetic exhaust gases near stoichiometry. In a first series of measurements, conversion rates were determined as a function of temperature at stoichiometry. The partial pressure effect of O 2 , NO and H 2 O was then determined at constant temperature in the region of catalyst light-off. NO and mainly O 2 were shown to have a negative effect on the first terms of saturated alkane conversion under lean conditions. Water vapor has a positive effect in rich conditions (without SO 2 ), but is more pronounced for Pt-Rh than for a Pt catalyst. Finally, the role played by SO 2 in hydrocarbon conversion was evaluated

Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

2016-01-04

The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

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)

Effect of Electric Discharge on Properties of Nano-Particulate Catalyst for Plasma-Catalysis.

Science.gov (United States)

Lee, Chung Jun; Kim, Jip; Kim, Taegyu

2016-02-01

Heterogeneous catalytic processes have been used to produce hydrogen from hydrocarbons. However, high reforming temperature caused serious catalyst deteriorations and low energy efficiency. Recently, a plasma-catalyst hybrid process was used to reduce the reforming temperature and to improve the stability and durability of reforming catalysts. Effect of electric discharges on properties of nanoparticulate catalysts for plasma-catalysis was investigated in the present study. Catalyst-bed porosity was varied by packing catalyst beads with the different size in a reactor. Discharge power and onset voltage of the plasma were measured as the catalyst-bed porosity was varied. The effect of discharge voltage, frequency and voltage waveforms such as the sine, pulse and square was investigated. We found that the optimal porosity of the catalyst-bed exists to maximize the electric discharge. At a low porosity, the electric discharge was unstable to be sustained because the space between catalysts got narrow nearly close to the sheath region. On the other hand, at a high porosity, the electric discharge became weak because the plasma was not sufficient to interact with the surface of catalysts. The discharge power increased as the discharge voltage and frequency increased. The square waveform was more efficient than the sine and pulse one. At a high porosity, however, the effect of the voltage waveform was not considerable because the space between catalysts was too large for plasma to interact with the surface of catalysts.

Hydrocarbon fuel processing of micro solid oxide fuel cell systems[Dissertation 17455

Energy Technology Data Exchange (ETDEWEB)

Stutz, M. J.

2007-07-01

The scope of this thesis is the numerical and experimental investigation of the fuel processing of a micro solid oxide fuel cell (SOFC) running on hydrocarbon fuel. The goal is to enhance the overall system efficiency by optimization of the reforming process in the steady state and the improvement of the start-up process. Micro SOFC are a potential alternative to the currently used batteries in portable devices. Liquid butane in a cartridge could be the energy source. This dissertation is focused on the fuel processing of the system, namely the reforming and post-combusting processes. The reformer converts the hydrocarbon fuel to a hydrogen rich gas that can be utilized by the SOFC. The post-combustor depletes the toxic and/or explosive gases before leaving the exhaust. Chapter One presents a short introduction to the field of hydrocarbon fuel processing in micro solid oxide fuel cell systems, the next three chapters deal with computational modeling of the transport phenomena inside a micro-reformer, which leads to a better understanding of the chemistry and the physics therein, hence progress in the design and operation parameters. The experimental part (i.e. Chapter Five) of this thesis focuses on the feasibility of a novel hybrid start-up method of a fuel cell system that employs existing components as an additional heat source. In Chapter Two the effect of wall heat conduction on the syngas (hydrogen and carbon monoxide) production of a micro-reformer, representing micro-fabricated channels or monoliths, is investigated. Methane is used as a model hydrocarbon fuel since its heterogeneous reaction path on rhodium is known and validated. The simulations demonstrate that the axial wall conduction strongly influences the performance of the micro-reformer and should not be neglected without a careful a priori investigation of its impact. Methane conversion and hydrogen yield are strongly dependent of the wall inner surface temperature, which is influenced by the

Catalytic performance of activated carbon supported cobalt catalyst for CO2 reforming of CH4.

Science.gov (United States)

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

2014-11-01

Syngas production by CO2 reforming of CH4 in a fixed bed reactor was investigated over a series of activated carbon (AC) supported Co catalysts as a function of Co loading (between 15 and 30wt.%) and calcination temperature (Tc=300, 400 or 500°C). The catalytic performance was assessed through CH4 and CO2 conversions and long-term stability. XRD and SEM were used to characterize the catalysts. It was found that the stability of Co/AC catalysts was strongly dependent on the Co loading and calcination temperature. For the loadings (25wt.% for Tc=300°C), stable activities have been achieved. The loading of excess Co (>wt.% 25) causes negative effects not only on the performance of the catalysts but also on the support surface properties. In addition, the experiment showed that ultrasound can enhance and promote dispersion of the active metal on the carrier, thus improving the catalytic performance of the catalyst. The catalyst activity can be long-term stably maintained, and no obvious deactivation has been observed in the first 2700min. After analyzing the characteristics, a reaction mechanism for CO2 reforming of CH4 over Co/AC catalyst was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

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...

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-01-15

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

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

International Nuclear Information System (INIS)

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

2017-01-01

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

PdZnAl Catalysts for the Reactions of Water-Gas-Shift, Methanol Steam Reforming, and Reverse-Water-Gas-Shift

Energy Technology Data Exchange (ETDEWEB)

Dagle, Robert A.; Platon, Alexandru; Datye, Abhaya K.; Vohs, John M.; Wang, Yong; Palo, Daniel R.

2008-03-07

Pd/ZnO/Al2O3 catalysts were studied for water-gas-shift (WGS), methanol steam reforming, and reverse-water-gas-shift (RWGS) reactions. WGS activity was found to be dependent on the Pd:Zn ratio with a maximum activity obtained at approximately 0.50, which was comparable to that of a commercial Pt-based catalyst. The catalyst stability was demonstrated for 100 hours time-on-stream at a temperature of 3600C without evidence of metal sintering. WGS reaction rates were approximately 1st order with respect to CO concentration, and kinetic parameters were determined to be Ea = 58.3 kJ mol-1 and k0 = 6.1x107 min-1. During methanol steam reforming, the CO selectivities were observed to be lower than the calculated equilibrium values over a range of temperatures and steam/carbon ratios studied while the reaction rate constants were approximately of the same magnitude for both WGS and methanol steam reforming. These results indicate that although Pd/ZnO/Al2O3 are active WGS catalysts, WGS is not involved in methanol steam reforming. RWGS rate constants are on the order of about 20 times lower than that of methanol steam reforming, suggesting that RWGS reaction could be one of the sources for small amount of CO formation in methanol steam reforming.

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

International Nuclear Information System (INIS)

Sutthisripok, W.; Laosiripojana, N.

2004-01-01

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

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

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

Science.gov (United States)

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

Reforming of Ethanol to Produce Hydrogen over PtRuMg/ZrO2 Catalyst

Directory of Open Access Journals (Sweden)

Josh Y. Z. Chiou

2012-01-01

Full Text Available A modified PtRu/ZrO2 catalyst with Mg is evaluated for the oxidative steam reforming of ethanol (OSRE and the steam reforming of ethanol (SRE. In order to understand the variation in the reaction mechanism on OSRE and SRE, further analysis of both fresh and used catalyst is concentrated on for TEM, TG, Raman, and TPR characterization. The results show that the OSRE reaction requires a higher temperature (∼390°C to achieve 100% ethanol conversion than the SRE reaction (∼2500°C. The distribution of CO is minor for both reactions (< 5% for OSRE, < 1% for SRE. This demonstrates that the water gas shift (WGS reaction is an important side-reaction in the reforming of ethanol to produce H2 and CO2. A comparison of the temperature of WGS (WGS shows it is lower for the SRE reaction (WGS∼250°C for SRE, ~340°C for OSRE.

Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

Science.gov (United States)

Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

2013-07-16

The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

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.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

International Nuclear Information System (INIS)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

2017-01-01

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

2017-11-14

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

Process and catalysts for hydrocarbon conversion. [high antiknock motor fuel

Energy Technology Data Exchange (ETDEWEB)

1940-02-14

High anti-knock motor fuel is produced from hydrocarbons by subjecting it at an elevated temperature to contact with a calcined mixture of hydrated silica, hydrated alumina, and hydrated zirconia, substantially free from alkali metal compounds. The catalyst may be prepared by precipitating silica gel by the acidification of an aqueous solution of an alkali metal silicate, intimately mixing hydrated alumina and hydrated zirconia therewith, drying, purifying the composite to substantially remove alkali metal compounds, again drying, forming the dried material into particles, and finally calcining. The resultant conversion products may be fractionated to produce gasoline, hydrocarbon oil above gasoling boiling point range, and a gaseous fraction of olefins which are polymerized into gasoline boiling range polymers.

Reforming options for hydrogen production from fossil fuels for PEM fuel cells

Energy Technology Data Exchange (ETDEWEB)

Ersoz, Atilla; Olgun, Hayati [TUBITAK Marmara Research Center, Institute of Energy, Gebze, 41470 Kocaeli (Turkey); Ozdogan, Sibel [Marmara University Faculty of Engineering, Goztepe, 81040 Istanbul (Turkey)

2006-03-09

PEM fuel cell systems are considered as a sustainable option for the future transport sector in the future. There is great interest in converting current hydrocarbon based transportation fuels into hydrogen rich gases acceptable by PEM fuel cells on-board of vehicles. In this paper, we compare the results of our simulation studies for 100kW PEM fuel cell systems utilizing three different major reforming technologies, namely steam reforming (SREF), partial oxidation (POX) and autothermal reforming (ATR). Natural gas, gasoline and diesel are the selected hydrocarbon fuels. It is desired to investigate the effect of the selected fuel reforming options on the overall fuel cell system efficiency, which depends on the fuel processing, PEM fuel cell and auxiliary system efficiencies. The Aspen-HYSYS 3.1 code has been used for simulation purposes. Process parameters of fuel preparation steps have been determined considering the limitations set by the catalysts and hydrocarbons involved. Results indicate that fuel properties, fuel processing system and its operation parameters, and PEM fuel cell characteristics all affect the overall system efficiencies. Steam reforming appears as the most efficient fuel preparation option for all investigated fuels. Natural gas with steam reforming shows the highest fuel cell system efficiency. Good heat integration within the fuel cell system is absolutely necessary to achieve acceptable overall system efficiencies. (author)

Reforming options for hydrogen production from fossil fuels for PEM fuel cells

Science.gov (United States)

Ersoz, Atilla; Olgun, Hayati; Ozdogan, Sibel

PEM fuel cell systems are considered as a sustainable option for the future transport sector in the future. There is great interest in converting current hydrocarbon based transportation fuels into hydrogen rich gases acceptable by PEM fuel cells on-board of vehicles. In this paper, we compare the results of our simulation studies for 100 kW PEM fuel cell systems utilizing three different major reforming technologies, namely steam reforming (SREF), partial oxidation (POX) and autothermal reforming (ATR). Natural gas, gasoline and diesel are the selected hydrocarbon fuels. It is desired to investigate the effect of the selected fuel reforming options on the overall fuel cell system efficiency, which depends on the fuel processing, PEM fuel cell and auxiliary system efficiencies. The Aspen-HYSYS 3.1 code has been used for simulation purposes. Process parameters of fuel preparation steps have been determined considering the limitations set by the catalysts and hydrocarbons involved. Results indicate that fuel properties, fuel processing system and its operation parameters, and PEM fuel cell characteristics all affect the overall system efficiencies. Steam reforming appears as the most efficient fuel preparation option for all investigated fuels. Natural gas with steam reforming shows the highest fuel cell system efficiency. Good heat integration within the fuel cell system is absolutely necessary to achieve acceptable overall system efficiencies.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-01-06

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

Improving Catalyst Efficiency in Bio-Based Hydrocarbon Fuels; NREL (National Renewable Energy Laboratory)

Energy Technology Data Exchange (ETDEWEB)

None

2015-06-01

This article investigates upgrading biomass pyrolysis vapors to form hydrocarbon fuels and chemicals using catalysts with different concentrations of acid sites. It shows that greater separation of acid sites makes catalysts more efficient at producing hydrocarbon fuels and chemicals. The conversion of biomass into liquid transportation fuels has attracted significant attention because of depleting fossil fuel reserves and environmental concerns resulting from the use of fossil fuels. Biomass is a renewable resource, which is abundant worldwide and can potentially be exploited to produce transportation fuels that are less damaging to the environment. This renewable resource consists of cellulose (40–50%), hemicellulose (25–35%), and lignin (16–33%) biopolymers in addition to smaller quantities of inorganic materials such as silica and alkali and alkaline earth metals (calcium and potassium). Fast pyrolysis is an attractive thermochemical technology for converting biomass into precursors for hydrocarbon fuels because it produces up to 75 wt% bio-oil,1 which can be upgraded to feedstocks and/or blendstocks for further refining to finished fuels. Bio-oil that has not been upgraded has limited applications because of the presence of oxygen-containing functional groups, derived from cellulose, hemicellulose and lignin, which gives rise to high acidity, high viscosity, low heating value, immiscibility with hydrocarbons and aging during storage. Ex situ catalytic vapor phase upgrading is a promising approach for improving the properties of bio-oil. The goal of this process is to reject oxygen and produce a bio-oil with improved properties for subsequent downstream conversion to hydrocarbons.

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-06-10

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-07-13

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

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

Science.gov (United States)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rh-Ni and Rh-Co Catalysts for Autothermal Reforming of Gasoline

Energy Technology Data Exchange (ETDEWEB)

Jung, Yeongyu; Lee, Daehyung; Kim, Yongmin; Lee, Jinhee; Nam, Sukwoo; Choi, Daeki; Yoon, Chang Won [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

2014-01-15

Rh doped Ni and Co catalysts, Rh-M/CeO{sub 2}(20 wt %)-Al{sub 2}O{sub 3} (0.2 wt % of Rh; M = Ni or Co, 20 wt %) were synthesized to produce hydrogen via autothermal reforming (ATR) of commercial gasoline at 700 .deg. C under the conditions of a S/C ratio of 2.0, an O/C ratio of 0.84, and a gas hourly space velocity (GHSV) of 20,000 h{sup -1}. The Rh-Ni/CeO{sub 2}(20 wt %)-Al{sub 2}O{sub 3} catalyst (1) exhibited excellent activities, with H{sub 2} and (H{sub 2}+CO) yields of 2.04 and 2.58 mol/mol C, respectively. In addition, this catalyst proved to be highly stable over 100 h without catalyst deactivation, as evidenced by energy dispersive spectroscopy (EDX) and elemental analyses. Compared to 1, Rh-Co/CeO{sub 2}(20 wt %)-Al{sub 2}O{sub 3} catalyst (2) exhibited relatively low stability, and its activity decreased after 57 h. In line with this observation, elemental analyses confirmed that nearly no carbon species were formed at 1 while carbon deposits (10 wt %) were found at 2 following the reaction, which suggests that carbon coking is the main process for catalyst deactivation.

Hydrodeoxygenation of bio-derived phenols to hydrocarbons using RANEY Ni and Nafion/SiO2 catalysts.

Science.gov (United States)

Zhao, Chen; Kou, Yuan; Lemonidou, Angeliki A; Li, Xuebing; Lercher, Johannes A

2010-01-21

A simple, green, cost- and energy-efficient route for converting phenolic components in bio-oil to hydrocarbons and methanol has been developed, with nearly 100% yields. In the heterogeneous catalysts, RANEY Ni acts as the hydrogenation catalyst and Nafion/SiO(2) acts as the Brønsted solid acid for hydrolysis and dehydration.

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....

A Phenomenological Study on the Synergistic Role of Precious Metals in the Steam Reforming of Logistic Fuels on Bimetal-Supported Catalysts

Directory of Open Access Journals (Sweden)

Abdul-Majeed Azad

2011-01-01

Full Text Available Fuel processors are required to convert sulfur-laden logistic fuels into hydrogen-rich reformate and deliver to the fuel cell stack with little or no sulfur. Since sulfur poisons and deactivates the reforming catalyst, robust sulfur-tolerant catalysts ought to be developed. In this paper, the development, characterization and evaluation of a series of reforming catalysts containing two noble metals (with total metal loading not exceeding 1 weight percent supported on nanoscale ceria for the steam-reforming of kerosene is reported. Due to inherent synergy, a bimetallic catalyst is superior to its monometallic analog, for the same level of loading. The choice of noble metal combination in the bimetallic formulations plays a vital and meaningful role in their performance. Presence of ruthenium and/or rhodium in formulations containing palladium showed improved sulfur tolerance and significant enhancement in their catalytic activity and stability. Rhodium was responsible for higher hydrogen yields in the logistic fuel reformate. Duration of steady hydrogen production was higher in the case of RhPd (75 h than for RuPd (68 h; hydrogen generation was stable over the longest period (88 h with RuRh containing no Pd. A mechanistic correlation between the characteristic role of precious metals in the presence of each other is discussed.

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.

Liquid and Gaseous Fuel from Waste Plastics by Sequential Pyrolysis and Catalytic Reforming Processes over Indonesian Natural Zeolite Catalysts

Directory of Open Access Journals (Sweden)

Mochamad Syamsiro

2014-08-01

Full Text Available In this study, the performance of several differently treated natural zeolites in a sequential pyrolysis and catalytic reforming of plastic materials i.e. polypropylene (PP and polystyrene (PS were investigated. The experiments were carried out on two stage reactor using semi-batch system. The samples were degraded at 500°C in the pyrolysis reactor and then reformed at 450°C in the catalytic reformer. The results show that the mordenite-type natural zeolites could be used as efficient catalysts for the conversion of PP and PS into liquid and gaseous fuel. The treatment of natural zeolites in HCl solution showed an increase of the surface area and the Si/Al ratio while nickel impregnation increased the activity of catalyst. As a result, liquid product was reduced while gaseous product was increased. For PP, the fraction of gasoline (C5-C12 increased in the presence of catalysts. Natural zeolite catalysts could also be used to decrease the heavy oil fraction (>C20. The gaseous products were found that propene was dominated in all conditions. For PS, propane and propene were the main components of gases in the presence of nickel impregnated natural zeolite catalyst. Propene was dominated in pyrolysis over natural zeolite catalyst. The high quality of gaseous product can be used as a fuel either for driving gas engines or for dual-fuel diesel engine.

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

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

International Nuclear Information System (INIS)

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

2009-01-01

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

Evaluation of Partial Oxidation Reformer Emissions

Energy Technology Data Exchange (ETDEWEB)

Unnasch, Stefan; Fable, Scott; Waterland, Larry

2006-01-06

In this study, a gasoline fuel processor and an ethanol fuel processor were operated under conditions simulating both startup and normal operation. Emissions were measured before and after the AGB in order to quantify the effectiveness of the burner catalyst in controlling emissions. The emissions sampling system includes CEM for O2, CO2, CO, NOx, and THC. Also, integrated gas samples are collected in evacuated canisters for hydrocarbon speciation analysis via GC. This analysis yields the concentrations of the hydrocarbon species required for the California NMOG calculation. The PM concentration in the anode burner exhaust was measured through the placement of a filter in the exhaust stream. The emissions from vehicles with fully developed on board reformer systems were estimated.

Aliphatic Hydrocarbons from Lignocellulose by Pyrolysis over Cesium-Modified Amorphous Silica Alumina Catalysts

NARCIS (Netherlands)

Zabeti, M.; Sai Sankar Gupta, Karthick Babu; Raman, G.; Lefferts, Leon; Schallmoser, Stefan; Lercher, Johannes A.; Seshan, K.

2015-01-01

Cesium-modified amorphous silica alumina (Cs/ASA) is a promising catalyst for the production of hydrocarbons through pyrolysis of biomass. Catalytic pyrolysis of pinewood over Cs/ASA in a pyrolyzer system in conjunction with a gas chromatograph and mass spectrometer resulted in a 22% yield of

Certain aspects of the formation and identification of nanosized oxide components in heterogeneous catalysts prepared by different methods

International Nuclear Information System (INIS)

Ellert, Ol'ga G; Novotortsev, Vladimir M; Tsodikov, Mark V

2010-01-01

The results of studies into the relationship 'methods and synthesis conditions of a catalyst→catalyst structure→catalytic properties' in highly efficient crystallo-graphically amorphous copper- and iron-containing heterogeneous systems obtained by different chemical methods are generalized. Polymorphism of active phases and catalytic properties of nanostructured copper-containing zinc, zirconium, manganese and cerium oxides are discussed. Unusual transformations of nanosized Pt- and Pd-containing components on the γ-Al 2 O 3 surface in nanostructured catalysts of ethanol steam reforming into synthesis gas and reductive dehydration of ethanol to alkanes are considered. The results of comparative studies on the crystallographically amorphous mixed iron oxide catalysts synthesized by either the alkoxy method or the deposition on various supports obtained by the Moessbauer and XAFS spectroscopy and magnetic susceptibility measurements are presented. These materials are shown to be efficient catalysts of important processes such as liquid-phase oxidation of hydrocarbons, synthesis of alkenes and alkylaromatic hydrocarbons from CO and H 2 , hydrogenative transformation of brown coal organic mass to hydrocarbons.

Hydrogen Production from Ethanol Steam Reforming over SnO2-K2O/Zeolite Y Catalyst

International Nuclear Information System (INIS)

Lee, Jun Sung; Kim, Ji Eun; Kang, Mi Sook

2011-01-01

The SnO 2 with a particle size of about 300 nm instead of Ni is used in this study to overcome rapid catalytic deactivation by the formation of a NiAl 2 O 4 spinal structure on the conventional Ni/γ-Al 2 O 3 catalyst and simultaneously impregnated the catalyst with potassium (K). The SnO 2 -K 2 O impregnated Zeolite Y catalyst (SnO 2 -K 2 O/ZY) exhibited significantly higher ethanol reforming reactivity that that achieved with SnO 2 100 and SnO 2 30 wt %/ZY catalysts. The main products from ethanol steam reforming (ESR) over the SnO 2 -K 2 O/ ZY catalyst were H 2 , CO 2 , and CH 4 , with no evidence of any CO molecule formation. The H 2 production and ethanol conversion were maximized at 89% and 100%, respectively, over SnO 2 30 wt %-K 2 O 3.0 wt %/ZY at 600 .deg. C for 1 h at a CH 3 CH 2 OH:H 2 O ratio of 1:1 and a gas hourly space velocity (GHSV) of 12,700 h -1 . No catalytic deactivation occurred for up to 73 h. This result is attributable to the easier and weaker of reduction of Sn components and acidities over SnO 2 -K 2 O/ZY catalyst, respectively, than those of Ni/γ-Al 2 O 3 catalysts

Co-current and Counter-Current Operations for Steam Reforming of Heptane in a Novel CFB Membrane Reformer

International Nuclear Information System (INIS)

Chen, Z.; Elnashaie, S.S.E.H.

2004-01-01

Hydrogen production by steam reforming of higher hydrocarbon over nickel supported catalyst is investigated in an earlier suggested novel Circulating Fast Fluidized Bed Membrane Reformer (CFFBMR). Palladium hydrogen membranes are used with co-current and counter-current operation modes. It is found that hydrogen production has a non-monotonic dependence upon the reaction temperature in the range of 623-823 K. Between 623 and 723 K. the yields of hydrogen decrease and then increase between 723 and 823 K. This important phenomenon is investigated, discussed and explained. The simulation results shows that the reformer performance can be significantly improved using hydrogen membranes, especially in the counter-current operation mode. At low temperatures around 623 K, both .co-current and counter-current operation modes provide similar yields of hydrogen. While at temperature 723 K and higher, the counter-current operation provides the highest yield of hydrogen

Hydrogen production by steam reforming of liquefied natural gas (LNG) over nickel catalysts supported on cationic surfactant-templated mesoporous aluminas

Science.gov (United States)

Seo, Jeong Gil; Youn, Min Hye; Park, Sunyoung; Jung, Ji Chul; Kim, Pil; Chung, Jin Suk; Song, In Kyu

Two types of mesoporous γ-aluminas (denoted as A-A and A-S) are prepared by a hydrothermal method under different basic conditions using cationic surfactant (cetyltrimethylammonium bromide, CTAB) as a templating agent. A-A and A-S are synthesized in a medium of ammonia solution and sodium hydroxide solution, respectively. Ni/γ-Al 2O 3 catalysts (Ni/A-A and Ni/A-S) are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of a mesoporous γ-Al 2O 3 support on the catalytic performance of Ni/γ-Al 2O 3 is investigated. The identity of basic solution strongly affects the physical properties of the A-A and A-S supports. The high surface-area of the mesoporous γ-aluminas and the strong metal-support interaction of supported catalysts greatly enhance the dispersion of nickel species on the catalyst surface. The well-developed mesopores of the Ni/A-A and Ni/A-S catalysts prohibit the polymerization of carbon species on the catalyst surface during the reaction. In the steam reforming of LNG, both Ni/A-A and Ni/A-S catalysts give better catalytic performance than the nickel catalyst supported on commercial γ-Al 2O 3 (Ni/A-C). In addition, the Ni/A-A catalyst is superior to the Ni/A-S catalyst. The relatively strong metal-support interaction of Ni/A-A catalyst effectively suppresses the sintering of metallic nickel and the carbon deposition in the steam reforming of LNG. The large pores of the Ni/A-A catalyst also play an important role in enhancing internal mass transfer during the reaction.

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.

Hydrogen Production from Methanol Steam Reforming over TiO2 and CeO2 Pillared Clay Supported Au Catalysts

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Rongbin Zhang

2018-01-01

Full Text Available Abstract: Methanol steam reforming is a promising process for the generation of hydrogen. In this study, Au catalysts supported on modified montmorillonite were prepared and their catalytic activity for methanol steam reforming was investigated at 250–500 °C. The physical and chemical properties of the as-prepared catalysts were characterized by Brunauer–Emmet–Teller method (BET, X-ray diffraction (XRD, transmission electron microscopic (TEM, scanning electron microscopy (SEM, X-ray photoelectron spectroscopy (XPS, Inductively Coupled Plasma (ICP, and thermogravimetrc analysis (TGA. For the catalysts examined, Au-Ti-Ce/Na-ABen exhibits the best catalytic performance with methanol conversion of 72% and H2 selectivity of 99% at 350 °C. This could be attributed to Au, Ce, and Ti species which form a solid solution and move into the interlayer space of the bentonite leading to a high surface area, large average pore volume, large average pore diameter, and small Au particle size. We considered that the synergistic effect of the crosslinking agent, the Ce species, and the Au active sites were responsible for the high activity of Au-Ti-Ce/Na-ABen catalyst for methanol steam reforming.

MECHANISTIC KINETIC MODELS FOR STEAM REFORMING OF CONCENTRATED CRUDE ETHANOL ON NI/AL2O3 CATALYST

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O. A. OLAFADEHAN

2015-05-01

Full Text Available Mechanistic kinetic models were postulated for the catalytic steam reforming of concentrated crude ethanol on a Ni-based commercial catalyst at atmosphere pressure in the temperature range of 673-863 K, and at different catalyst weight to the crude ethanol molar flow rate ratio (in the range 0.9645-9.6451 kg catalyst h/kg mole crude ethanol in a stainless steel packed bed tubular microreactor. The models were based on Langmuir-Hinshelwood-Hougen-Watson (LHHW and Eley-Rideal (ER mechanisms. The optimization routine of Nelder-Mead simplex algorithm was used to estimate the inherent kinetic parameters in the proposed models. The selection of the best kinetic model amongst the rival kinetic models was based on physicochemical, statistical and thermodynamic scrutinies. The rate determining step for the steam reforming of concentrated crude ethanol on Ni/Al2O3 catalyst was found to be surface reaction between chemisorbed CH3O and O when hydrogen and oxygen were adsorbed as monomolecular species on the catalyst surface. Excellent agreement was obtained between the experimental rate of reaction and conversion of crude ethanol, and the simulated results, with ADD% being ±0.46.

Effects of adding lanthanum to Ni/ZrO2 catalysts on ethanol steam reforming

International Nuclear Information System (INIS)

Profeti, Luciene Paula Roberto; Habitzheuter, Filipe; Assaf, Elisabete Moreira

2012-01-01

The catalytic performance of Ni/ZrO 2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting with the support, due to the higher dispersion effect. The best catalytic performance at 450 deg C was found for the Ni/12LZ catalyst, which exhibited an effluent gaseous mixture with the highest H 2 yield. (author)

Jet-Fuel Range Hydrocarbons from Biomass-Derived Sorbitol over Ni-HZSM-5/SBA-15 Catalyst

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Yujing Weng

2015-12-01

Full Text Available Aromatics and cyclic-hydrocarbons are the significant components of jet fuel with high energy-density. However, conventional technologies for bio-fuel production cannot produce these products without further aromatization and isomerization. In this work, renewable liquid fuel with high content of aromatics and cyclic-hydrocarbons was obtained through aqueous catalytic conversion of biomass sorbitol over Ni-HZSM-5/SBA-15 catalyst. Texture characteristics of the catalyst were determined by physisorption of N2, which indicated its bimodal pore structures were microporous (HZSM-5, pore width: 0.56 nm and mesoporous (SBA-15, pore width: 8 nm. The surface acidity included weak and strong acid sites, predominantly Lewis type, and was further confirmed by the NH3-TPD and Py-IR analysis. The catalytic performances were tested in a fixed-bed reactor under the conditions of 593 K, WHSV of 0.75 h−1, GHSV of 2500 h−1 and 4.0 MPa of hydrogen pressure, whereby oil yield of 40.4 wt. % with aromatics and cyclic-hydrocarbons content of 80.0% was obtained.

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.

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.

Catalytic Steam Reforming of Toluene as a Model Compound of Biomass Gasification Tar Using Ni-CeO2/SBA-15 Catalysts

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Erik Dahlquist

2013-07-01

Full Text Available Nickel supported on SBA-15 doped with CeO2 catalysts (Ni-CeO2/SBA-15 was prepared, and used for steam reforming of toluene which was selected as a model compound of biomass gasification tar. A fixed-bed lab-scale set was designed and employed to evaluate the catalytic performances of the Ni-CeO2/SBA-15 catalysts. Experiments were performed to reveal the effects of several factors on the toluene conversion and product gas composition, including the reaction temperature, steam/carbon (S/C ratio, and CeO2 loading content. Moreover, the catalysts were subjected to analysis of their carbon contents after the steam reforming experiments, as well as to test the catalytic stability over a long experimental period. The results indicated that the Ni-CeO2/SBA-15 catalysts exhibited promising capabilities on the toluene conversion, anti-coke deposition and catalytic stability. The toluene conversion reached as high as 98.9% at steam reforming temperature of 850 °C and S/C ratio of 3 using the Ni-CeO2(3wt%/SBA-15 catalyst. Negligible coke formation was detected on the used catalyst. The gaseous products mainly consisted of H2 and CO, together with a little CO2 and CH4.

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

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

Zeolites as Catalysts for Fuels Refining after Indirect Liquefaction Processes

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Arno de Klerk

2018-01-01

Full Text Available The use of zeolite catalysts for the refining of products from methanol synthesis and Fisher–Tropsch synthesis was reviewed. The focus was on fuels refining processes and differences in the application to indirect liquefaction products was compared to petroleum, which is often a case of managing different molecules. Processes covered were skeletal isomerisation of n-butenes, hydroisomerisation of n-butane, aliphatic alkylation, alkene oligomerisation, methanol to hydrocarbons, ethanol and heavier alcohols to hydrocarbons, carbonyls to hydrocarbons, etherification of alkenes with alcohols, light naphtha hydroisomerisation, catalytic naphtha reforming, hydroisomerisation of distillate, hydrocracking and fluid catalytic cracking. The zeolite types that are already industrially used were pointed out, as well as zeolite types that have future promise for specific conversion processes.

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

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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.

Remarkable support effect on the reactivity of Pt/In2O3/MOx catalysts for methanol steam reforming

Science.gov (United States)

Liu, Xin; Men, Yong; Wang, Jinguo; He, Rong; Wang, Yuanqiang

2017-10-01

Effects of supports over Pt/In2O3/MOx catalysts with extremely low loading of Pt (1 wt%) and In2O3 loadings (3 wt%) are investigated for the hydrogen production of methanol steam reforming (MSR) in the temperature range of 250-400 °C. Under practical conditions without the pre-reduction, the 1Pt/3In2O3/CeO2 catalyst shows the highly efficient catalytic performance, achieving almost complete methanol conversion (98.7%) and very low CO selectivity of 2.6% at 325 °C. The supported Pt/In2O3 catalysts are characterized by means of Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), high-resolution transmission microscopy (HRTEM), temperature programmed reduction with hydrogen (H2-TPR), CO pulse chemisorption, temperature programmed desorption of methanol and water (CH3OH-TPD and H2O-TPD). These demonstrate that the nature of catalyst support of Pt/In2O3/MOx plays crucial roles in the Pt dispersion associated by the strong interaction among Pt, In2O3 and supporting materials and the surface redox properties at low temperature, and thus affects their capability to activate the reactants and determines the catalytic activity of methanol steam reforming. The superior 1Pt/3In2O3/CeO2 catalyst, exhibiting a remarkable reactivity and stability for 32 h on stream, demonstrates its potential for efficient hydrogen production of methanol steam reforming in mobile and de-centralized H2-fueled PEMFC systems.

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

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.

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.

Cobalt catalysts for the conversion of methanol and for Fischer-tropsch synthesis to produce hydrocarbons

International Nuclear Information System (INIS)

Mauldin, C.H.; Davis, S.M.; Arcuri, K.B.

1987-01-01

A regeneration stable catalyst is described for the conversion at reaction conditions of methanol or synthesis gas to liquid hydrocarbons which consists essentially of from about 2 percent to about 25 percent cobalt, based on the weight of the catalyst composition, composited with titania, or a titania-containing support, to which is added sufficient of a zirconium, hafnium, cerium, or uranium promoter to provide a weight ratio of the zirconium, hafnium, cerium, or uranium metal:cobalt greater than about 0.101:1

Steam reforming of heptane in a fluidized bed membrane reactor

Science.gov (United States)

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

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

Syngas Conversion to Gasoline-Range Hydrocarbons over Pd/ZnO/Al2O3 and ZSM-5 Composite Catalyst System

Energy Technology Data Exchange (ETDEWEB)

Dagle, Robert A.; Lizarazo Adarme, Jair A.; Lebarbier, Vanessa MC; Gray, Michel J.; White, James F.; King, David L.; Palo, Daniel R.

2014-07-01

A composite Pd/ZnO/Al2O3-HZSM-5 (Si/Al=40) catalytic system was evaluated for the synthesis of gasoline-range hydrocarbons directly from synthesis gas. Bifunctional catalyst comprising PdZn metal and acid sites present the required catalytically active sites necessary for the methanol synthesis, methanol dehydration, and methanol-to-gasoline reactions. This system provides a unique catalytic pathway for the production of liquid hydrocarbons directly from syngas. However, selectivity control is difficult and poses many challenges. The composite catalytic system was evaluated under various process conditions. Investigated were the effects of temperature (310-375oC), pressure (300-1000 psig), time-on-stream (50 hrs), and gas-hour space velocity (740-2970 hr-1), using a H2/CO molar syngas ratio of 2.0. By operating at the lower end of the temperature range investigated, liquid hydrocarbon formation was favored, as was decreased amounts of undesirable light hydrocarbons. However, lower operating temperatures also facilitated undesirable CO2 formation via the water-gas shift reaction. Higher operating pressures slightly favored liquid synthesis. Operating at relatively low pressures (e.g. 300 psig) was made possible, whereas for methanol synthesis alone higher pressure are usually required to achieve similar conversion levels (e.g. 1000 psig). Thermodynamic constraints on methanol synthesis are eased by pushing the equilibrium through hydrocarbon formation. Catalytic performance was also evaluated by altering Pd and Zn composition of the Pd/ZnO/Al2O3 catalyst. Of the catalysts and conditions tested, selectivity toward liquid hydrocarbon was highest when using a 5% Pd metal loading and Pd/Zn molar ratio of 0.25 and mixed with HZMS-5, operating at 310oC and 300 psig, CO conversion was 43 % and selectivity (carbon weight basis) to hydrocarbons was 49 wt. %. Of the hydrocarbon fraction, 44wt. % was in the C5-C12 liquid product range and consisted primarily of aromatic

Deactivation Studies of Rh/Ce0.8Zr0.2O2 Catalysts in Low Temperature Ethanol Steam Reforming

Energy Technology Data Exchange (ETDEWEB)

Platon, Alex; Roh, Hyun-Seog; King, David L.; Wang, Yong

2007-10-30

Rapid deactivation of Rh/Ce0.8Zr0.2O2 catalysts in low temperature ethanol steam reforming was studied. A significant build-up of carbonaceous intermediate, instead of carbon deposit, was observed at a lower reaction temperature which was attributed to the rapid catalyst deactivation. Co-feed experiments indicated that acetone and ethylene caused more severe catalyst deactivation than other oxygenates such as acidic acid and acetaldehyde.

Syngas production from ethanol dry reforming over Rh/CeO2 catalyst

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Shulin Zhao

2018-01-01

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

Enhancing Pt-Ni/CeO2 performances for ethanol reforming by catalyst supporting on high surface silica

NARCIS (Netherlands)

Palma, V.; Ruocco, C; Meloni, E.; Gallucci, F.; Ricca, A.

2018-01-01

In this paper, bimetallic Pt-Ni/CeO2 catalysts supported over mesoporous silica were employed for ethanol reforming in the low-temperature range. In particular, catalyst behaviour was investigated under a H2O/C2H5OH/N2 as well as H2O/C2H5OH/AIR mixture between 300 and 600 °C at different space

Zn-Mo/HZSM-5 Catalyst for Gasoil Range Hydrocarbon Production by Catalytic Hydrocracking of Ceiba pentandra oil

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Yustia Wulandari Mirzayanti

2018-01-01

Full Text Available Biofuel from vegetable oil becomes one of the most suitable and logical alternatives to replace fossil fuel. The research focused on various metal ratio Zinc/Molybdenum/HZSM-5 (Zn-Mo/HZSM-5 catalyst to produce liquid hydrocarbon via catalytic hydrocracking of Ceiba penandra oil. The catalytic hydrocracking process has been applied in this study to crack Ceiba pentandra oil into a gasoil range hydrocarbon using Zn-Mo/HZSM-5 as a catalyst. The effect of various reaction temperature on the catalytic hydrocracking of Ceiba pentandra oil were studied. The Zn-Mo/HZSM-5 catalyst with metal ratio was prepared by incipient wetness impregnation method. This process used slurry pressure batch reactor with a mechanical stirrer. A series of experiments were carried out in the temperature range from 300-400 oC for 2 h at pressure between 10-15 bar. The conversion and selectivity were estimated. The liquid hydrocarbon product were identified to gasoline, kerosene, and gas oil. The results show that the use of Zn-Mo/HZSM-5 can produce gas oil as the most component in the product. Overall, the highest conversion and selectivity of gas oil range hydrocarbon was obtained when the ZnMo/HZSM-5 metal ratio was Zn(2.86 wt.%-Mo(5.32 wt.%/HZSM-5 and the name is Zn-Mo/HZSM-5_102. The highest conversion was obtained at 63.31 % and n-paraffin (gas oil range selectivity was obtained at 90.75 % at a temperature of 400 oC. Ceiba pentandra oil can be recommended as the source of inedible vegetable oil to produce gasoil as an environmentally friendly transportation fuel. Copyright © 2018 BCREC Group. All rights reserved Received: 8th September 2017; Revised: 9th September 2017; Accepted: 17th September 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Mirzayanti, Y.W., Kurniawansyah, F., Prajitno, D.H., Roesyadi, A. (2018. Zn-Mo/HZSM-5 Catalyst for Gasoil Range Hydrocarbon Production by Catalytic Hydrocracking of Ceiba pentandra

Analytical study on carbon dioxide reforming of natural gas

International Nuclear Information System (INIS)

Ohashi, Hirofumi; Sakaki, Akihiro; Inagaki, Yoshiyuki

2001-01-01

In recent years, considerable attention has been paid to carbon dioxide reforming of natural gas, namely CO 2 reforming, since it can produce synthesis gas with low hydrogen-to-carbon ratio preferentially used for production of liquid hydrocarbons in the Fischer-Tropsch and methanol syntheses. This reaction has also very important environmental implications because CO 2 , a green house gas, may be converted into valuable feedstock. In JAERI, CO 2 reforming using the out-of-pile test facility, which is a 1/30 scale model of the HTTR hydrogen production system, is also being considered as an application of steam reforming. For the purpose to estimate the reformer performance in the facility, numerical analysis of natural gas reforming processes of CO 2 and combined reactions with steam and CO 2 has been carried out using mathematical model on heat and mass balance accompanied by chemical reactions. The reformer performance was evaluated in the effect of pressure, temperature, process gas composition and reaction rate constants of the catalyst on conversion, product gas composition and heat consumption of He gas. And also, the potential of carbon formation by CH 4 cracking reaction and Boudouard reaction was estimated. (author)

Structured reactors as alternative to pellets catalyst for propane oxidative steam reforming

Energy Technology Data Exchange (ETDEWEB)

Vita, A.; Pino, L.; Cipiti, F.; Lagana, M.; Recupero, V. [CNR - Institute for Advanced Energy Technologies ' ' Nicola Giordano' ' , Via Salita S. Lucia sopra Contesse n. 5, 98126 Messina (Italy)

2010-09-15

The performance of a Pt/CeO{sub 2} catalyst as packed bed, coated on monolith and as self-structured bed has been evaluated during C{sub 3}H{sub 8} oxidative steam reforming. Structured bed, prepared by a new aqueous tape casting method, combining high total porosity (80%) with a self-supported channel structure, offers a better and more efficient control of heat and mass transfer along the catalytic bed, showing, especially at high gas hourly space velocity (30 x 10{sup 4} h{sup -1}), better performance in terms of fuel conversion, hydrogen production and low by-products formation coupled with an economy of the catalyst of about to 43% with respect to the traditional packed bed system. (author)

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.

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)

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

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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

Solar central receiver reformer system for ammonia plants

Science.gov (United States)

1980-07-01

Details of the conceptual design, economic analysis, and development plan for a solar central receiver system for retrofitting the Valley Nitrogen Producers, Inc., El Centro, California 600 ST/SD Ammonia Plant are presented. The retrofit system consists of a solar central receiver reformer (SCRR) operating in parallel with the existing fossil fired reformer. Steam and hydrocarbon react in the catalyst filled tubes of the inner cavity receiver to form a hydrogen rich mixture which is the syngas feed for the ammonia production. The SCRR system displaces natural gas presently used in the fossil reformer combustion chamber. The solar reformer retrofit system characteristics and its interface with the existing plant are simple, incorporating state of the art components with proven technology. A northfield composed of one thousand forty second generation heliostats provides solar energy to the receiver which is positioned on top of a 90 meter high steel tower. The overall economics of this system can provide over 20% discount cash flow rate of return with proper investment and market conditions.

Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

Directory of Open Access Journals (Sweden)

Véronique Pitchon

2012-02-01

Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

Methanol Reforming over Cobalt Catalysts Prepared from Fumarate Precursors: TPD Investigation

Directory of Open Access Journals (Sweden)

Eftichia Papadopoulou

2016-02-01

Full Text Available Temperature-programmed desorption (TPD was employed to investigate adsorption characteristics of CH3OH, H2O, H2, CO2 and CO on cobalt-manganese oxide catalysts prepared through mixed Co-Mn fumarate precursors either by pyrolysis or oxidation and oxidation/reduction pretreatment. Pyrolysis temperature and Co/Mn ratio were the variable synthesis parameters. Adsorption of methanol, water and CO2 was carried out at room temperature. Adsorption of H2 and H2O was carried out at 25 and 300 °C. Adsorption of CO was carried out at 25 and 150 °C. The goal of the work was to gain insight on the observed differences in the performance of the aforementioned catalysts in methanol steam reforming. TPD results indicated that activity differences are mostly related to variation in the number density of active sites, which are able to adsorb and decompose methanol.

Process for refining hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Risenfeld, E H

1924-11-26

A process is disclosed for the refining of hydrocarbons or other mixtures through treatment in vapor form with metal catalysts, characterized by such metals being used as catalysts, which are obtained by reduction of the oxide of minerals containing the iron group, and by the vapors of the hydrocarbons, in the presence of the water vapor, being led over these catalysts at temperatures from 200 to 300/sup 0/C.

Bifurcation behavior during the hydrogen production in two compatible configurations of a novel circulating fluidized bed membrane reformer

International Nuclear Information System (INIS)

Chen, Z.; Elnashaie, S.S.

2004-01-01

'Full text:' Multiplicity of steady states (Static Bifurcation Behavior, SBB) in a novel Circulating Fluidized Bed (CFB) membrane reformer for the efficient production of hydrogen by steam reforming of heptane (model component of heavy hydrocarbons and renewable bio-oils) is investigated. The present paper highlights the practical implications of this phenomenon on the behavior of this novel reformer with special focusing on hydrogen production. Two configurations are considered and compared. One is with the catalyst regeneration before the gas-solid separation and the other one is with the catalyst regeneration after the gas-solid separation. Multiplicity of the steady states prevails over a number of design and operating parameters with important impact on the reformer performance. The basis of process evaluation is focused on the net hydrogen production. The dependence of the behavior of this autothermal CFB is shown to be quite complex and defy the simple logic of non-autothermal processes. The unit can be a very efficient hydrogen producer provided its bifurcation behavior is well understood and correctly exploited. (author)

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...

Catalytic conversion of alcohols to hydrocarbons with low benzene content

Energy Technology Data Exchange (ETDEWEB)

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-03-08

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

Energy Technology Data Exchange (ETDEWEB)

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-09-06

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Methanol steam reforming over Pd/ZnO and Pd/CeO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, Easwar S.; Bej, Shyamal K.; Thompson, Levi T. [University of Michigan, Department of Chemical Engineering, 3026 H.H. Dow Building, 2300 Hayward Avenue, Ann Arbor, MI 48109-2136 (United States)

2005-08-10

The goal of work described in this paper was to better understand the methanol steam reforming (MSR) activity and selectivity patterns of ZnO and CeO{sub 2} supported Pd catalysts. This reaction is being used to produce H{sub 2}-rich gas for a number of applications including hydrogen fuel cells. The Pd/ZnO catalysts had lower MSR rates but were more selective for the production of CO{sub 2} than the Pd/CeO{sub 2} catalysts. The CH{sub 3}OH conversion rates were proportional to the H{sub 2} chemisorption uptake suggesting that the rate determining step was catalyzed by Pd. The corresponding turnover frequencies averaged 0.8+/-0.3s{sup -1} and 0.4+/-0.2s{sup -1} at 230{sup o}C for the Pd/ZnO and Pd/CeO{sub 2} catalysts, respectively. The selectivities are explained based on the reaction pathways, and characteristics of the support. The key surface intermediate appeared to be a formate. The ZnO supported catalysts had a higher density of acidic sites and favored pathways where the intermediate was converted to CO{sub 2} while the CeO{sub 2} supported catalysts had a higher density of basic sites and favored the production of CO.

Steam reformer with catalytic combustor

Science.gov (United States)

Voecks, Gerald E. (Inventor)

1990-01-01

A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

Influence of the Crystal Structure of Titanium Oxide on the Catalytic Activity of Rh/TiO2 in Steam Reforming of Propane at Low Temperature.

Science.gov (United States)

Yu, Lin; Sato, Katsutoshi; Toriyama, Takaaki; Yamamoto, Tomokazu; Matsumura, Syo; Nagaoka, Katsutoshi

2018-05-01

Solid oxide fuel cells (SOFCs) using liquefied petroleum gas(LPG) reduce CO2 emissions due to their high energy-conversion efficiency. Although SOFCs can convert LPG directly, coking occurs easily by decomposition of hydrocarbons, including C-C bonds on the electrode of fuel cell stacks. It is therefore necessary to develop an active steam pre-reforming catalyst that eliminates the hydrocarbons at low temperature, where waste heat of SOFCs is used. Here we show that the crystal structure of the TiO2 that anchors Rh particles is crucial for catalytic activity of Rh/TiO2 catalysts for propane pre-reforming. Our experimental results revealed that strong metal support interaction (SMSI) induced during H2 pre-reduction were optimized over Rh/TiO2 with a rutile structure; this catalyst catalyzed the reaction much more effectively than conventional Rh/γ-Al2O3. In contrast, the SMSI was too strong for Rh/TiO2 with an anatase structure, and the surface of the Rh particles was therefore covered mostly with partially reduced TiO2. The result was very low activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Catalytic activity of cobalt and cerium catalysts supported on calcium hydroxyapatite in ethanol steam reforming

Directory of Open Access Journals (Sweden)

Dobosz Justyna

2016-09-01

Full Text Available In this paper, Co,Ce/Ca10(PO46(OH2 catalysts with various cobalt loadings for steam reforming of ethanol (SRE were prepared by microwave-assisted hydrothermal and sol-gel methods, and characterized by XRD, TEM, TPR-H2, N2 adsorption-desorption measurements and cyclohexanol (CHOL decomposition tests. High ethanol conversion (close to 100% was obtained for the catalysts prepared by both methods but these ones prepared under hydrothermal conditions (HAp-H ensured higher hydrogen yield (3.49 mol H2/mol C2H5OH as well as higher amount of hydrogen formed (up to 70% under reaction conditions. The superior performance of 5Co,10Ce/HAp-H catalyst is thought to be due to a combination of factors, including increased reducibility and oxygen mobility, higher density of basic sites on its surface, and improved textural properties. The results also show a significant effect of cobalt loading on catalysts efficiency in hydrogen production: the higher H2 yield exhibit catalysts with lower cobalt content, regardless of the used synthesis method.

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

Science.gov (United States)

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

2002-08-01

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

Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts

Energy Technology Data Exchange (ETDEWEB)

Han, Jun; Zhan, Yiqiu; Street, Jason; To, Filip; Yu, Fei

2017-07-01

A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO₂ (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni₁₀CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH₄ and CO₂ decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni10CeAl catalyst was performed using BET, H₂-TPR, in-situ XRD, TEM, and TGA-DTG techniques. The in-situ XRD results revealed that Ce₂O₃, CeO₂ and CeAlO₃ coexisted in the Ni10CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.

Steam reforming of commercial ultra-low sulphur diesel

Energy Technology Data Exchange (ETDEWEB)

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

2011-03-11

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

Steam reforming of commercial ultra-low sulphur diesel

Science.gov (United States)

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

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

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.

Effect of Ce and Zr Addition to Ni/SiO2 Catalysts for Hydrogen Production through Ethanol Steam Reforming

Directory of Open Access Journals (Sweden)

Jose Antonio Calles

2015-01-01

Full Text Available A series of Ni/Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\/SiO\\(_{2}\\ catalysts with different Zr/Ce mass ratios were prepared by incipient wetness impregnation. Ni/SiO\\(_{2}\\, Ni/CeO\\(_{2}\\ and Ni/ZrO\\(_{2}\\ were also prepared as reference materials to compare. Catalysts' performances were tested in ethanol steam reforming for hydrogen production and characterized by XRD, H\\(_{2}\\-temperature programmed reduction (TPR, NH\\(_{3}\\-temperature programmed desorption (TPD, TEM, ICP-AES and N\\(_{2}\\-sorption measurements. The Ni/SiO\\(_{2}\\ catalyst led to a higher hydrogen selectivity than Ni/CeO\\(_{2}\\ and Ni/ZrO\\(_{2}\\, but it could not maintain complete ethanol conversion due to deactivation. The incorporation of Ce or Zr prior to Ni on the silica support resulted in catalysts with better performance for steam reforming, keeping complete ethanol conversion over time. When both Zr and Ce were incorporated into the catalyst, Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\ solid solution was formed, as confirmed by XRD analyses. TPR results revealed stronger Ni-support interaction in the Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\-modified catalysts than in Ni/SiO\\(_{2}\\ one, which can be attributed to an increase of the dispersion of Ni species. All of the Ni/Ce\\(_{x}\\Zr\\(_{1-x}\\O\\(_{2}\\/SiO\\(_{2}\\ catalysts exhibited good catalytic activity and stability after 8 h of time on stream at 600°. The best catalytic performance in terms of hydrogen selectivity was achieved when the Zr/Ce mass ratio was three.

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.)

Reforming process. Reformierungsverfahren

Energy Technology Data Exchange (ETDEWEB)

McCoy, C.S.

1982-05-19

A naphta fraction is subjected to a catalytic reforming process in several series-connected reactors. The first reactor is equipped with a moving catalyst bed containing not more the 30% of volume of the total catalyst amount. The other reactors are designed as packed-bed systems. The content of coke deposited on the catalyst of the first reactor owing to the reforming process is maintained at below 1% of weight. This is effected by periodic removal of a proportion of the contaminated catalyst from the bottom part of the bed, by its regeneration and re-feeding to the top part of the bed. This results in prolonged service life of the catalyst and simultaneous improvement of the anti-knock value of the product.

Liquid phase in situ hydrodeoxygenation of biomass-derived phenolic compounds to hydrocarbons over bifunctional catalysts

Science.gov (United States)

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

2017-01-01

The objective of this study was to find an effective method for converting renewable biomass-derived phenolic compounds into hydrocarbons bio-fuel via in situ catalytic hydrodeoxygenation. The in situ hydrodeoxygenation of biomass-derived phenolic compounds was carried out in methanol-water solvent over bifunctional catalysts of Raney Ni and HZSM-5 or H-Beta. In the in...

Microwave plasmas generated in bubbles immersed in liquids for hydrocarbons reforming

International Nuclear Information System (INIS)

Levko, Dmitry; Sharma, Ashish; Raja, Laxminarayan L

2016-01-01

We present a computational modeling study of microwave plasma generated in cluster of atmospheric-pressure argon bubbles immersed in a liquid. We demonstrate that the use of microwaves allows the generation of a dense chemically active non-equilibrium plasma along the gas–liquid interface. Also, microwaves allow generation of overdense plasma in all the bubbles considered in the cluster which is possible because the collisional skin depth of the wave exceeds the bubble dimension. These features of microwave plasma generation in bubbles immersed in liquids are highly desirable for the large-scale liquid hydrocarbon reforming technologies. (letter)

Highly selective bimetallic Pt-Cu/Mg(Al)O catalysts for the aqueous-phase reforming of glycerol

NARCIS (Netherlands)

Boga, D.A.; Oord, R.; Beale, A.M.; Chung, Y.M.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

2013-01-01

Monometallic Pt and bimetallic Pt-Cu catalysts supported on Mg(Al)O mixed oxides, obtained by calcination of the corresponding layered double hydroxides (LDHs), were prepared and tested in the aqueous-phase reforming (APR) of glycerol. The effect of the Mg/Al ratio and calcination temperature of the

Synthesis of Hydrocarbons from H2-Deficient Syngas in Fischer-Tropsch Synthesis over Co-Based Catalyst Coupled with Fe-Based Catalyst as Water-Gas Shift Reaction

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Ting Ma

2015-01-01

Full Text Available The effects of metal species in an Fe-based catalyst on structural properties were investigated through the synthesis of Fe-based catalysts containing various metal species such, as Mn, Zr, and Ce. The addition of the metal species to the Fe-based catalyst resulted in high dispersions of the Fe species and high surface areas due to the formation of mesoporous voids about 2–4 nm surrounded by the catalyst particles. The metal-added Fe-based catalysts were employed together with Co-loaded beta zeolite for the synthesis of hydrocarbons from syngas with a lower H2/CO ratio of 1 than the stoichiometric H2/CO ratio of 2 for the Fischer-Tropsch synthesis (FTS. Among the catalysts, the Mn-added Fe-based catalyst exhibited a high activity for the water-gas shift (WGS reaction with a comparative durability, leading to the enhancement of the CO hydrogenation in the FTS in comparison with Co-loaded beta zeolite alone. Furthermore, the loading of Pd on the Mn-added Fe-based catalyst enhanced the catalytic durability due to the hydrogenation of carbonaceous species by the hydrogen activated over Pd.

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

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Nur Nabillah Mohd Arif

2016-08-01

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

Paraselectivity and Formation of Aromatic Hydrocarbons over ZSM-5 Type Catalysts

Energy Technology Data Exchange (ETDEWEB)

Unneberg, E

1997-12-31

The zeolite ZSM-5, patented by Mobil Oil Corporation in 1972, is able to convert methanol to gasoline (MTG) and water. Due to the size of the channels, undesired hydrocarbons larger than C{sub 11} are not present in the mixture, and a high octane gasoline is obtained. This has aroused a great deal of interest in the ZSM-5. Rather than being concerned with energy considerations, this doctoral thesis describes syntheses of ZSM-5 and discusses the ZSM-5 as such and studies the possible paraselectivities in various reactions over the catalyst ZSM-5. 774 refs., 113 figs., 54 tabs.

Paraselectivity and Formation of Aromatic Hydrocarbons over ZSM-5 Type Catalysts

Energy Technology Data Exchange (ETDEWEB)

Unneberg, E.

1996-12-31

The zeolite ZSM-5, patented by Mobil Oil Corporation in 1972, is able to convert methanol to gasoline (MTG) and water. Due to the size of the channels, undesired hydrocarbons larger than C{sub 11} are not present in the mixture, and a high octane gasoline is obtained. This has aroused a great deal of interest in the ZSM-5. Rather than being concerned with energy considerations, this doctoral thesis describes syntheses of ZSM-5 and discusses the ZSM-5 as such and studies the possible paraselectivities in various reactions over the catalyst ZSM-5. 774 refs., 113 figs., 54 tabs.

Hydrogen production from raw bioethanol steam reforming: optimization of catalyst composition with improved stability against various impurities

International Nuclear Information System (INIS)

Le Valant, A.; Can, F.; Bion, N.; Epron, F.; Duprez, D.

2009-01-01

Usually, ethanol steam reforming is performed using pure ethanol, whereas the use of raw bioethanol is of major importance for a cost effective industrial application. Raw bioethanol contains higher alcohols as the main impurities and also aldehydes, amines, acids and esters. The effect of these impurities on the catalytic performances for ethanol steam reforming (ESR) has been studied, using a reference catalyst, Rh/MgAl 2 O 4 . It was shown that the aldehyde, the amine and methanol has no negative effect on the catalytic performances, contrary to the ester, acid and higher alcohols. The deactivation is mainly explained by coke formation favored by the presence of these impurities in the feed. In order to improve the stability of the catalyst and its performances in the presence of these deactivating impurities, the catalyst formulation, i.e. the composition of the support and of the metallic phase, was modified. The addition of rare earth elements instead of magnesium to the alumina support leads to a decrease of the strong and medium acid sites and to an increase of the basicity. On these modified supports, the dehydration reaction, leading to olefins, which are coke precursors, is disfavored, the ethanol conversion and the hydrogen yield are increased. The best catalytic performances were obtained with Rh/Y-Al 2 O 3 . Then, the metallic phase was also modified by adding a second metal (Ni, Pt or Pd). The Rh-Ni/Y-Al 2 O 3 catalyst leads to the highest hydrogen yield. This catalyst, tested in the presence of raw bioethanol during 24h was very stable compared to the reference catalyst Rh/MgAl 2 O 4 , which was strongly deactivated after 2h of time-on-stream. (author)

Experimental evaluation of a Pt based heat exchanger methanol reformer for a HTPEM fuel cell

DEFF Research Database (Denmark)

Andreasen, Søren Juhl; Nielsen, Mads Pagh; Kær, Søren Knudsen

2007-01-01

The storage of hydrogen in hydrogen consuming applications is often inconvenient because of the very low density of hydrogen even at high pressures (0.014 kg/L @ 300 bar) or cryogenically (0.043 kg/L). Much higher volumetric energy densities can be achieved using liquid hydrocarbons as e.g. metha...... (up to 1-2%). This work examines the possibility of using a catalyst coated plate heat exchanger for the reforming process of methanol....

High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

Energy Technology Data Exchange (ETDEWEB)

Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

2016-12-01

High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

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

Kinetics study of ethanol steam reforming on Pt/CeO{sub 2} based catalysts

Energy Technology Data Exchange (ETDEWEB)

Qi, A. [Queen' s-RMC Fuel Cell Research Centre, Kingston, ON (Canada). Dept. of Chemistry and Chemical Engineering; Thurgood, C.; Amphlett, J. [Royal Military College of Canada, Kingston, ON (Canada). Dept. of Chemistry and Chemical Engineering; Peppley, B. [Queens Univ., Kingston, ON (Canada). Dept. of Chemical Engineering

2009-07-01

Interest in fuel cell systems operating on fuels derived from renewable energy sources is increasing because they have the potential to produce electricity with high efficiency and minimal emissions of carbon dioxide and other pollutants. Bioethanol is currently produced by the fermentation of non-edible biomass, through conventional means and also through advances in enzyme technology. The authors previously reported on the steam reforming of bioethanol with a stable ceria supported precious metal catalyst, developed in-house. The catalyst had good thermal stability and resisted carbon formation. This paper reported on a more recent kinetic study in which the influence of operating conditions were quantified. The operating conditions included temperature, steam/carbon ratios, and gas hourly velocities. The results of standard catalyst characterization techniques such as BET, TGA, SEM and TPR were also provided. The data was used to drive an empirical rate expression. The study also investigated a potential rate mechanism.

Valorization of biogas into liquid hydrocarbons in plasma-catalyst reactor

Science.gov (United States)

Nikravech, Mehrdad; Rahmani, Abdelkader; Labidi, Sana; Saintini, Noiric

2016-09-01

Biogas represents an important source of renewable energy issued from biological degradation of biomass. It is planned to produce in Europe the amount of biogas equivalent to 6400 kWh electricity and 4500 kteo (kilo tons equivalent oil) in 2020. Currently the biogas is used in cogeneration engines to produce heat and electricity directly in farms or it is injected in gas networks after purification and odorisation. The aim of this work is to propose a third option that consists of valorization of biogas by transformation into liquid hydrocarbons like acetone, methanol, ethanol, acetic acid etc. These chemicals, among the most important feed materials for chemical industries, retain CO2 molecules participating to reduce the greenhouse gas emissions and have high storage energy capacity. We developed a low temperature atmospheric plasma-catalyst reactor (surface dielectric barrier discharge) to transform biogas into chemicals. The conversion rates of CH4 and CO2 are respectively about 50% and 30% depending on operational conditions. The energetic cost is 25 eV/molecule. The yields of liquid hydrocarbon reaches currently 10% wt. More the 11 liquid chemicals are observed in the liquid fraction. Acknowledgements are due to SPC Programme Energie de demain.

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.)

Steam reforming of methanol over oxide decorated nanoporous gold catalysts: a combined in situ FTIR and flow reactor study.

Science.gov (United States)

Shi, J; Mahr, C; Murshed, M M; Gesing, T M; Rosenauer, A; Bäumer, M; Wittstock, A

2017-03-29

Methanol as a green and renewable resource can be used to generate hydrogen by reforming, i.e., its catalytic oxidation with water. In combination with a fuel cell this hydrogen can be converted into electrical energy, a favorable concept, in particular for mobile applications. Its realization requires the development of novel types of structured catalysts, applicable in small scale reactor designs. Here, three different types of such catalysts were investigated for the steam reforming of methanol (SRM). Oxides such as TiO 2 and CeO 2 and mixtures thereof (Ce 1 Ti 2 O x ) were deposited inside a bulk nanoporous gold (npAu) material using wet chemical impregnation procedures. Transmission electron and scanning electron microscopy reveal oxide nanoparticles (1-2 nm in size) abundantly covering the strongly curved surface of the nanoporous gold host (ligaments and pores on the order of 40 nm in size). These catalysts were investigated in a laboratory scaled flow reactor. First conversion of methanol was detected at 200 °C. The measured turn over frequency at 300 °C of the CeO x /npAu catalyst was 0.06 s -1 . Parallel investigation by in situ infrared spectroscopy (DRIFTS) reveals that the activation of water and the formation of OH ads are the key to the activity/selectivity of the catalysts. While all catalysts generate sufficient OH ads to prevent complete dehydrogenation of methanol to CO, only the most active catalysts (e.g., CeO x /npAu) show direct reaction with formic acid and its decomposition to CO 2 and H 2 . The combination of flow reactor studies and in operando DRIFTS, thus, opens the door to further development of this type of catalyst.

Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons.

Science.gov (United States)

Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian; Ju, Wen; Oh, Hyung-Suk; Strasser, Peter

2015-09-07

This study explores the kinetics, mechanism, and active sites of the CO2 electroreduction reaction (CO2RR) to syngas and hydrocarbons on a class of functionalized solid carbon-based catalysts. Commercial carbon blacks were functionalized with nitrogen and Fe and/or Mn ions using pyrolysis and acid leaching. The resulting solid powder catalysts were found to be active and highly CO selective electrocatalysts in the electroreduction of CO2 to CO/H2 mixtures outperforming a low-area polycrystalline gold benchmark. Unspecific with respect to the nature of the metal, CO production is believed to occur on nitrogen functionalities in competition with hydrogen evolution. Evidence is provided that sufficiently strong interaction between CO and the metal enables the protonation of CO and the formation of hydrocarbons. Our results highlight a promising new class of low-cost, abundant electrocatalysts for synthetic fuel production from CO2 . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characteristics of mordenite-type zeolite catalysts deactivated by SO{sub 2} for the reduction of NO with hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Kim, M.H.; Nam, I.S.; Kim, Y.G. [Pohang Univ. of Science and Technology/Research Inst. of Industrial Science and Technology, Pohang (Korea, Republic of)

1998-10-25

The deactivation of mordenite-type zeolite catalysts for the selective reduction of NO by hydrocarbons in the presence of SO{sub 2} was examined in a packed-bed flow reactor system. The physicochemical properties of the deactivated catalysts by SO{sub 2} were extensively characterized by TGA, TPSR, XPS, Raman, XANES, the measurements of surface area and elemental analysis. Not only the surface area and sulfur content of the deactivated catalysts, but their TGA and TPSR patterns strongly suggest the formation of a sulfur species as a deactivating agent on the catalyst surface. It is also observed that the sulfur species exists in the form of sulfate (SO{sub 4}{sup 2{minus}}) by XPS and Raman. It mainly causes the loss of NO removal activity of the catalysts. The sulfate species formed on the deactivated catalysts by SO{sub 2} did not significantly alter the chemical environment of the copper ions contained in the zeolite catalysts such as CuHM and CuNZA. It does not exist in the form of cupric sulfate pentahydrate on the catalyst surface as revealed by Cu K-edge absorption spectra of the catalysts.

High-temperature catalytic reforming of n-hexane over supported and core-shell Pt nanoparticle catalysts: role of oxide-metal interface and thermal stability.

Science.gov (United States)

An, Kwangjin; Zhang, Qiao; Alayoglu, Selim; Musselwhite, Nathan; Shin, Jae-Youn; Somorjai, Gabor A

2014-08-13

Designing catalysts with high thermal stability and resistance to deactivation while simultaneously maintaining their catalytic activity and selectivity is of key importance in high-temperature reforming reactions. We prepared Pt nanoparticle catalysts supported on either mesoporous SiO2 or TiO2. Sandwich-type Pt core@shell catalysts (SiO2@Pt@SiO2 and SiO2@Pt@TiO2) were also synthesized from Pt nanoparticles deposited on SiO2 spheres, which were encapsulated by either mesoporous SiO2 or TiO2 shells. n-Hexane reforming was carried out over these four catalysts at 240-500 °C with a hexane/H2 ratio of 1:5 to investigate thermal stability and the role of the support. For the production of high-octane gasoline, branched C6 isomers are more highly desired than other cyclic, aromatic, and cracking products. Over Pt/TiO2 catalyst, production of 2-methylpentane and 3-methylpentane via isomerization was increased selectively up to 420 °C by charge transfer at Pt-TiO2 interfaces, as compared to Pt/SiO2. When thermal stability was compared between supported catalysts and sandwich-type core@shell catalysts, the Pt/SiO2 catalyst suffered sintering above 400 °C, whereas the SiO2@Pt@SiO2 catalyst preserved the Pt nanoparticle size and shape up to 500 °C. The SiO2@Pt@TiO2 catalyst led to Pt nanoparticle sintering due to incomplete protection of the TiO2 shells during the reaction at 500 °C. Interestingly, over the Pt/TiO2 catalyst, the average size of Pt nanoparticles was maintained even after 500 °C without sintering. In situ ambient pressure X-ray photoelectron spectroscopy demonstrated that the Pt/TiO2 catalyst did not exhibit TiO2 overgrowth on the Pt surface or deactivation by Pt sintering up to 600 °C. The extraordinarily high stability of the Pt/TiO2 catalyst promoted high reaction rates (2.0 μmol · g(-1) · s(-1)), which was 8 times greater than other catalysts and high isomer selectivity (53.0% of C6 isomers at 440 °C). By the strong metal-support interaction

Production of Renewable Hydrogen from Glycerol Steam Reforming over Bimetallic Ni-(Cu,Co,Cr Catalysts Supported on SBA-15 Silica

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Alicia Carrero

2017-02-01

Full Text Available Glycerol steam reforming (GSR is a promising alternative to obtain renewable hydrogen and help the economics of the biodiesel industry. Nickel-based catalysts are typically used in reforming reactions. However, the choice of the catalyst greatly influences the process, so the development of bimetallic catalysts is a research topic of relevant interest. In this work, the effect of adding Cu, Co, and Cr to the formulation of Ni/SBA-15 catalysts for hydrogen production by GSR has been studied, looking for an enhancement of its catalytic performance. Bimetallic Ni-M/SBA-15 (M: Co, Cu, Cr samples were prepared by incipient wetness co-impregnation to reach 15 wt % of Ni and 4 wt % of the second metal. Catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES, N2-physisorption, X-ray powder diffraction (XRD, hydrogen temperature programmed reduction (H2-TPR, transmission electron microscopy (TEM, scanning electron microscopy (SEM, and thermogravimetric analyses (TGA, and tested in GSR at 600 °C and atmospheric pressure. The addition of Cu, Co, and Cr to the Ni/SBA-15 catalyst helped to form smaller crystallites of the Ni phase, this effect being more pronounced in the case of the Ni-Cr/SBA-15 sample. This catalyst also showed a reduction profile shifted towards higher temperatures, indicating stronger metal-support interaction. As a consequence, the Ni-Cr/SBA-15 catalyst exhibited the best performance in GSR in terms of glycerol conversion and hydrogen production. Additionally, Ni-Cr/SBA-15 achieved a drastic reduction in coke formation compared to the Ni/SBA-15 material.

Synthesis and Activity Test of Cu/ZnO/Al2O3 for the Methanol Steam Reforming as a Fuel Cell’s Hydrogen Supplier

Directory of Open Access Journals (Sweden)

IGBN Makertihartha

2009-05-01

Full Text Available The synthesis of hydrogen from hydrocarbons through the steam reforming of methanol on Cu/ZnO/Al2O3 catalyst has been investigated. This process is assigned to be one of the promising alternatives for fuel cell hydrogen process source. Hydrogen synthesis from methanol can be carried out by means of methanol steam reforming which is a gas phase catalytic reaction between methanol and water. In this research, the Cu/ZnO/Al2O3 catalyst prepared by the dry impregnation was used. The specific surface area of catalyst was 194.69 m2/gram.The methanol steam reforming (SRM reaction was carried out by means of the injection of gas mixture containing methanol and water with 1:1.2 mol ratio and 20-90 mL/minute feed flow rate to a fixed bed reactor loaded by 1 g of catalyst. The reaction temperature was 200-300 °C, and the reactor pressure was 1 atm. Preceding the reaction, catalyst was reduced in the H2/N2 mixture at 160 °C. This study shows that at 300 °C reaction temperature, methanol conversion reached 100% at 28 mL/minute gas flow rate. This conversion decreased significantly with the increase of gas flow rate. Meanwhile, the catalyst prepared for SRM was stable in 36 hours of operation at 260 °C. The catalyst exhibited a good stability although the reaction condition was shifted to a higher gas flow rate.

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

Hydrogen Production by Steam Reforming of Ethanol over Nickel Catalysts Supported on Sol Gel Made Alumina: Influence of Calcination Temperature on Supports.

Science.gov (United States)

Yaakob, Zahira; Bshish, Ahmed; Ebshish, Ali; Tasirin, Siti Masrinda; Alhasan, Fatah H

2013-05-30

Selecting a proper support in the catalyst system plays an important role in hydrogen production via ethanol steam reforming. In this study, sol gel made alumina supports prepared for nickel (Ni) catalysts were calcined at different temperatures. A series of (Ni/Al S.G. ) catalysts were synthesized by an impregnation procedure. The influence of varying the calcination temperature of the sol gel made supports on catalyst activity was tested in ethanol reforming reaction. The characteristics of the sol gel alumina supports and Ni catalysts were affected by the calcination temperature of the supports. The structure of the sol gel made alumina supports was transformed in the order of γ → (γ + θ) → θ-alumina as the calcination temperature of the supports increased from 600 °C to 1000 °C. Both hydrogen yield and ethanol conversion presented a volcano-shaped behavior with maximum values of 4.3 mol/mol ethanol fed and 99.5%, respectively. The optimum values were exhibited over Ni/Al S.G800 (Ni catalyst supported on sol gel made alumina calcined at 800 °C). The high performance of the Ni/Al S.G800 catalyst may be attributed to the strong interaction of Ni species and sol gel made alumina which lead to high nickel dispersion and small particle size.

Hydrogen-Rich Gas Production by Sorption Enhanced Steam Reforming of Woodgas Containing TAR over a Commercial Ni Catalyst and Calcined Dolomite as CO2 Sorbent

Directory of Open Access Journals (Sweden)

Vincenzo Naso

2013-07-01

Full Text Available The aim of this work was the evaluation of the catalytic steam reforming of a gaseous fuel obtained by steam biomass gasification to convert topping atmosphere residue (TAR and CH4 and to produce pure H2 by means of a CO2 sorbent. This experimental work deals with the demonstration of the practical feasibility of such concepts, using a real woodgas obtained from fluidized bed steam gasification of hazelnut shells. This study evaluates the use of a commercial Ni catalyst and calcined dolomite (CaO/MgO. The bed material simultaneously acts as reforming catalyst and CO2 sorbent. The experimental investigations have been carried out in a fixed bed micro-reactor rig using a slipstream from the gasifier to evaluate gas cleaning and upgrading options. The reforming/sorption tests were carried out at 650 °C while regeneration of the sorbent was carried out at 850 °C in a nitrogen environment. Both combinations of catalyst and sorbent are very effective in TAR and CH4 removal, with conversions near 100%, while the simultaneous CO2 sorption effectively enhances the water gas shift reaction producing a gas with a hydrogen volume fraction of over 90%. Multicycle tests of reforming/CO2 capture and regeneration were performed to verify the stability of the catalysts and sorbents to remove TAR and capture CO2 during the duty cycle.

Characterization of catalysts Rh and Ni/CexZr1-xO2 for hydrogen production by ethanol steam reforming

International Nuclear Information System (INIS)

Birot, A.

2005-01-01

This work concerned a study on catalytic behaviour of metallic catalysts (Rh or Ni) supported on earth rare oxides Ce x Zr 1-x O 2 in ethanol steam reforming in order to produce hydrogen. Catalyst 1%Rh/Ce0,50Zr0,50O 2 showed a good activity with a good hydrogen yield. We turned a study onto understanding inter-conversion reaction between H 2 , CO and CO 2 which lead to CH 4 formation. We also studied intrinsic properties of catalysts. We confirmed basic character of catalysts and a good hydrogenation activity. A good activity in CO hydrogenation allowed to evidence a necessity to use a catalyst which is less active in hydrogenation reaction and with a basic character in order to improve hydrogen yield. (author)

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)

Formation of hydrocarbon compounds during the hydrocracking of non-edible vegetable oils with cobalt-nickel supported on hierarchical HZSM-5 catalyst

Science.gov (United States)

Marlinda, L.; Al-Muttaqii, M.; Roesyadi, A.; Prajitno, D. H.

2017-05-01

The hierarchical Co-Ni/HZSM-5 catalyst with hierarchical pore structure was prepared by desilication and incipient wetness impregnation. Hydrocracking of non-edible vegetable oils at temperature of 400 °C, 20±5 bar for 2 h was performed in the presence of this type of catalyst under hydrogen initial pressure in pressured batch reactor. Non-edible vegetable oils, such as Reutealis trisperma (Blanco) airy shaw (sunan candlenut) and Hevea brasiliensis (rubber seed) were chosen to study the effect of the degree of saturation and lateral chain length on hydrocarbon compounds obtained through hydrocracking. Cerbera manghas oil was also tested for comparison because the composition of fatty acid was different with the other oils The hydrocracking test indicated that liquid product produced has a similar hydrocarbon compounds with petroleum diesel. The most abundant hydrocarbon is pentadecane (n-C15) and heptadecane (n-C17). The high aromatic compounds were found in liquid product produced in hydrocracking of Sunan candlenut oil.

Procedure for manufacturing pipes with wall catalyst especially for steam reforming of hydrocarbons and to obtain methane

Energy Technology Data Exchange (ETDEWEB)

Golebiowski, A; Paluch-Paluch, S; Janecki, Z; Polanski, A; Hennel, W; Zielinski, J; Warzec, C; Lisowski, W

1978-07-13

Pipes with a wall catalyst must retain a firm connection between the wall and the catalyst system even at high temperatures. According to the invention, this can be achieved if a metal sponge is produced on the pipe wall using an electrolytic process, in which ceramic and catalytic materials are included. The manufacture of the pipes is explained by 7 examples.

Spatial Distribution of Zeolite ZSM-5 within Catalyst Bodies Affects Selectivity and Stability of Methanol-to-Hydrocarbons Conversion

NARCIS (Netherlands)

Castaño, P.; Ruiz-Martinez, J.; Epelde, E.; Gayubo, A.G.; Weckhuysen, B.M.

2013-01-01

Solid acids, such as zeolites, are used as catalyst materials in a wide variety of important crude oil refinery, bulk chemical synthesis, and green processes. Examples include fluid catalytic cracking (FCC),[1] methanol-to-hydrocarbons (MTH) conversion,[ 2] plastic waste valorization,[3] and biomass

Highly stable and active Ni-doped ordered mesoporous carbon catalyst on the steam reforming of ethanol application

Directory of Open Access Journals (Sweden)

Josh Y.Z. Chiou

2017-02-01

Full Text Available A novel one-step direct synthesis of nickel embedded in an ordered mesoporous carbon catalyst (NiOMC is done in a basic medium of nonaqueous solution by a solvent evaporation-induced self-assembly process. The NiOMC sample is characterized by a variety of analytical and spectroscopy techniques, e.g., N2 adsorption/desorption isotherm measurement, X-ray diffraction (XRD, transmission electron microscopy (TEM and temperature-programed reduction (TPR. In this study, the NiOMC catalyst is found to exhibit superior catalytic activity for the steam reforming of ethanol (SRE, showing high hydrogen selectivity and durability. Ethanol can be completely converted at 350 °C over the NiOMC catalyst. Also, the durability of the NiOMC catalyst on the SRE reaction exceeds 100 h at 450 °C, with SH2 approaching 65% and SCO of less than 1%.

Selective hydrodeoxygenation of biomass-derived oxygenates to unsaturated hydrocarbons using molybdenum carbide catalysts.

Science.gov (United States)

Ren, Hui; Yu, Weiting; Salciccioli, Michael; Chen, Ying; Huang, Yulin; Xiong, Ke; Vlachos, Dionisios G; Chen, Jingguang G

2013-05-01

Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Hydrogen Production by Ethanol Steam Reforming (ESR over CeO2 Supported Transition Metal (Fe, Co, Ni, Cu Catalysts: Insight into the Structure-Activity Relationship

Directory of Open Access Journals (Sweden)

Michalis Konsolakis

2016-03-01

Full Text Available The aim of the present work was to investigate steam reforming of ethanol with regard to H2 production over transition metal catalysts supported on CeO2. Various parameters concerning the effect of temperature (400–800 °C, steam-to-carbon (S/C feed ratio (0.5, 1.5, 3, 6, metal entity (Fe, Co, Ni, Cu and metal loading (15–30 wt.% on the catalytic performance, were thoroughly studied. The optimal performance was obtained for the 20 wt.% Co/CeO2 catalyst, achieving a H2 yield of up to 66% at 400 °C. In addition, the Co/CeO2 catalyst demonstrated excellent stability performance in the whole examined temperature range of 400–800 °C. In contrast, a notable stability degradation, especially at low temperatures, was observed for Ni-, Cu-, and Fe-based catalysts, ascribed mainly to carbon deposition. An extensive characterization study, involving N2 adsorption-desorption (BET, X-ray diffraction (XRD, Scanning Electron Microscopy (SEM/EDS, X-ray Photoelectron Spectroscopy (XPS, and Temperature Programmed Reduction (H2-TPR was undertaken to gain insight into the structure-activity correlation. The excellent reforming performance of Co/CeO2 catalysts could be attributed to their intrinsic reactivity towards ethanol reforming in combination to their high surface oxygen concentration, which hinders the deposition of carbonaceous species.

Catalysts for synthetic liquid fuels

Energy Technology Data Exchange (ETDEWEB)

Bruce, L.A.; Turney, T.W.

1987-12-01

Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

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

Science.gov (United States)

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

2017-12-20

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

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.

Hydrogen production from steam reforming of ethanol over Ni/MgO-CeO_2 catalyst at low temperature

Institute of Scientific and Technical Information of China (English)

石秋杰; 刘承伟; 谌伟庆

2009-01-01

MgO,CeO2 and MgO-CeO2 with different mole ratio of Mg:Ce were prepared by solid-phase burning method.Catalysts Ni/MgO,Ni/CeO2 and Ni/MgO-CeO2 were prepared by impregnation method.The catalytic properties were evaluated in ethanol steam reforming(ESR) reaction.Specific surface areas of the supports were measured by nitrogen adsorption-desorption at 77 K,and the catalysts were characterized with X-ray diffraction(XRD),temperature programmed reduction(TPR) and thermogravimetric(TG).The results showed that well...

Catalyst Deactivation and Regeneration Processes in Biogas Tri-Reforming Process. The Effect of Hydrogen Sulfide Addition

Directory of Open Access Journals (Sweden)

Urko Izquierdo

2018-01-01

Full Text Available This work studies Ni-based catalyst deactivation and regeneration processes in the presence of H2S under a biogas tri-reforming process for hydrogen production, which is an energy vector of great interest. 25 ppm of hydrogen sulfide were continuously added to the system in order to provoke an observable catalyst deactivation, and once fully deactivated two different regeneration processes were studied: a self-regeneration and a regeneration by low temperature oxidation. For that purpose, several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on alumina modified with CeO2 and ZrO2 were used as well as a commercial Katalco 57-5 for comparison purposes. Ni/Ce-Al2O3 and Ni/Ce-Zr-Al2O3 catalysts almost recovered their initial activity. For these catalysts, after the regeneration under oxidative conditions at low temperature, the CO2 conversions achieved—79.5% and 86.9%, respectively—were significantly higher than the ones obtained before sulfur poisoning—66.7% and 45.2%, respectively. This effect could be attributed to the support modification with CeO2 and the higher selectivity achieved for the Reverse Water-Gas-Shift (rWGS reaction after catalysts deactivation. As expected, the bimetallic Rh-Ni/Ce-Al2O3 catalyst showed higher resistance to deactivation and its sulfur poisoning seems to be reversible. In the case of the commercial and Ni/Zr-Al2O3 catalysts, they did not recover their activity.

Maximum utilization of primary reformer catalyst tubes careful assessment of remaining life-An experience at an ammonia plant

International Nuclear Information System (INIS)

Malik, M.A.

2005-01-01

Condition evaluation and residual life assessment of Reformer Catalyst Tubes has always been a point of concern for Ammonia and Methanol Plant operators. Failure of catalyst tubes results in total plant shutdown and consequent production loss. On the other hand, replacement of these tubes entails major cost impact on the company's budget, being a capital expenditure. A careful Residual Life Assessment of the tubes is therefore of utmost importance for maximum utilization of these tubes without jeopardizing plant operational reliability. This paper presents an experience of extracting maximum service life from the catalyst tubes of Primary Reformer of an Ammonia Plant. Fauji Fertilizer Company (FFC) has been operating the plant since 1982, having a designed capacity of 1100 MTPD. Its Primary Reformer has 288 catalyst tubes of IN-519 material (24Cr-24Ni-Nb). The design temperature and pressures are 925 degree C and 38kg/Cm respectively. Thanks to the optimum operating conditions, regular inspections and careful assessment of the residual life, the tubes have achieved more than double of the designed life and are still operating reliably. To evaluate the tube's health, Ultrasonic Inspection (UT) was carried out in 1987 and 1994 using attenuation technique. The tubes with maximum attenuation were marked for further evaluation. Accelerated Creep Rupture Test was carried out on sample tubes periodically (1996, 2001 and 2004). Tubes were selected on the basis of UT results, TMT (Tube Metal Temperature) monitoring and Inspection findings. Based on the combined results of DT, NDT, equipment history and foreseen operational parameters, the life of these tubes was carefully assessed periodically. The tubes have been in service for more than 23 years (design life: 11 years) and a further life of 04 years has been predicted as per last assessment.The experience of successful health evaluation and residual life assessment has saved substantial cost involved in tubes replacement

Mixed reforming of simulated gasoline to hydrogen in a BSCFO membrane reactor

Energy Technology Data Exchange (ETDEWEB)

Zhu, Wenliang; Han, Wei; Xiong, Guoxing; Yang, Weishen [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P.O. Box 110, Dalian 116023 (China)

2006-10-30

Currently, fuel cells are receiving more and more attention as the most promising new power generation technology, and fuel processing by the mixed reforming of liquid hydrocarbons (MRL) with water and oxygen is regarded as a desirable way for fuel cells. In this paper, we developed a new mixed reforming method for hydrogen production by combining a dense ceramic membrane Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}}(BSCFO) with a catalyst LiLaNiO/{gamma}-Al{sub 2}O{sub 3} in a membrane reactor and reforming a simulated gasoline. During a 500-h long-term test at optimized reaction conditions, all the components in the simulated gasoline converted completely, and around 90% selectivity of CO, around 95% selectivity of H{sub 2} and around 8.0mLcm{sup -2}min{sup -1} oxygen permeation flux were achieved. This provides a new optional way of hydrogen production for fuel cells. (author)

Removal of CO from reformate for PEFC application.

Energy Technology Data Exchange (ETDEWEB)

Lee, S. H. D.

1998-09-14

Polymer electrolyte fuel cells (PEFCs) are being actively developed worldwide for transportation applications. The fuel gas generated from reforming hydrocarbon fuels contains small amounts of CO (0.5-1 vol%), even after the water-gas shift reaction. Carbon monoxide is preferentially adsorbed on the platinum electrocatalyst in the PEFC, thus blocking the access of H{sub 2} to the surface of the catalyst and resulting in the degradation of the cell performance. Therefore, the CO concentration in the PBFC reformate must be reduced to a tolerable level of {le} 100 ppm (1). Catalytic preferential oxidation (2), anode air bleed (3), or a combination of the two can be used to reduce CO to trace levels, but their use in a dynamically varying system is problematic. We are developing a sorption process based on the reversible complex-forming and dissociation reactions of CO with Cu(I). These reactions are well documented in patent and literature (4,5).

Carbon monoxide tolerant anodes for proton exchange membrane (PEM) fuel cells. 1. Catalyst development approach

Energy Technology Data Exchange (ETDEWEB)

Holleck, G L; Pasquariello, D M; Clauson, S L

1998-07-01

PEM fuel cells are highly attractive for distributed power and cogeneration systems. They are efficient and function virtually without noise or pollution. To be competitive PEM fuel cells must operate on fuel mixtures obtained by reforming of widely available natural gas or liquid hydrocarbons. Reformed fuel gas mixtures invariably contain CO, a strong poison for Pt. Therefore CO tolerant anode catalysts are essential for wide spread PEMFC introduction. It is the objective to develop effective CO tolerant fuel cell catalysts based on multi-component platinum-transition metal alloys. Towards this goal the authors have developed a novel approach for the synthesis and performance evaluation of multifunctional ternary alloy fuel cell catalysts. The alloys are prepared as well-defined thin films on standard TFE-bonded carbon substrates via a dc magnetron sputtering technique. The anodes are laminated to Nafion membranes and the electrochemical performance is measured in a representative fuel cell configuration with H{sub 2} and H{sub 2}/CO gas mixtures. The multi-target sputtering technique permits one to reproducibly synthesize true alloy films of controlled composition. The deposit morphology and electrode structure are determined by the standardized TFE bonded carbon substrate. The thin catalyst layer is concentrated at the electrode ionomer interface where it can be fully utilized in a representative fuel cell configuration. Thus, a true comparative fuel cell catalyst evaluation is possible. The effectiveness of this approach will be demonstrated with Pt, Pt-Ru and Pt-Ru-X catalyzed anodes.

Deoxygenation of palm kernel oil to jet fuel-like hydrocarbons using Ni-MoS_2/γ-Al_2O_3 catalysts

International Nuclear Information System (INIS)

Itthibenchapong, Vorranutch; Srifa, Atthapon; Kaewmeesri, Rungnapa; Kidkhunthod, Pinit; Faungnawakij, Kajornsak

2017-01-01

Highlights: • The Ni-MoS_2/γ-Al_2O_3 catalysts synthesized using thiourea solution processing. • The Ni-MoS_2 showed semi-amorphous crystallinity with crystallite size of 5–10 nm. • The Ni K-edge XANES and EXAFS indicated the Ni substitution in MoS_2 structure. • A high yield of jet fuel-like hydrocarbon (>90%) from the palm kernel oil feedstock. • The HDO pathway was highly selective, while the DCO_2 and DCO pathways were minor. - Abstract: In the current study, palm kernel oil was used as a renewable feedstock for production of jet fuel-like hydrocarbons via the deoxygenation over the Ni-MoS_2/γ-Al_2O_3 catalyst. The dominant C12 fatty acid content in palm kernel oil makes it promising for jet fuel application. Synthesized by a liquid processing method with thiourea organosulfur agent, the catalyst revealed MoS_2 structure with low stacking, while Ni substitution in the MoS_2 structure and interaction with the Al_2O_3 support were determined based on the Ni K-edge XANES and EXAFS results. A high hydrodeoxygenation (HDO) activity, which as the major pathway in the deoxygenation, was observed upon application of a H_2 pressure of 30–50 bar over Ni-MoS_2/γ-Al_2O_3. The optimum product yield of approximately 92% was obtained mainly from the HDO pathway (∼60%) with 58% selectivity to C10–C12 jet fuel hydrocarbons. The flow property of the jet fuel-like hydrocarbons was more desirable than those obtained from palm olein oil-derived fuel.

Steam reforming: an old process for a new solution; Le vaporeformage catalytique: un vieux procede pour une solution nouvelle...

Energy Technology Data Exchange (ETDEWEB)

Aupretre, F.; Descorme, C.; Duprez, D. [Poitiers Univ., Lab. de Catalyse en Chimie Organique, LACCO, UMR CNRS 6503, 86 (France)

2000-07-01

A bibliographic review allows to understand very quickly the stake that the electric-powered vehicle represents. The research of a hydrogen production process answering to the demands of the fuel cell application is then one of the main stakes. The catalytic steam reforming of hydrocarbons or of alcohols is a very promising way. The choices of ethanol and of rhodium based catalysts supported on oxides with strong oxygen mobility will be entirely justified because of the physico-chemical characteristics of the ethanol, of the reaction mechanism, of the cerium based oxide catalyst and of the specifications involved in the fuel cell application. (O.M.)

Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

Science.gov (United States)

Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

2016-09-01

The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

Hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1927-02-22

Coal tar, mineral oils, bitumens, coal extraction products, hydrogenation products of coal, oil schists can be atomized and heated with steam to decompose pyrogenetically and form gases rich in olefins which may be heated with or without pressure and with or without catalysts to produce liquid hydrocarbons of low boiling point, some of which may be aromatic. The apparatus should be lined with copper, silica, or ferrosilicon to prevent contact of the bases with iron which causes deposition of soot. Catalysts used may be metal oxides, silica, graphite, active charcoal, mica, pumice, porcelain, barium carbonate, copper, silver, gold, chromium, boron, or their compounds. At temperatures from 300 to 400/sup 0/C, olefins are produced. At higher temperatures, naphthenes and benzene hydrocarbons are produced.

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

Directory of Open Access Journals (Sweden)

M. Anwar Hossain

2018-01-01

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

Hydrogen production by methanol steam reforming carried out in membrane reactor on Cu/Zn/Mg-based catalyst

NARCIS (Netherlands)

Basile, A.; Parmaliana, A.; Tosti, S.; Iulianelli, A.; Gallucci, F.; Espro, C.; Spooren, J.

2008-01-01

The methanol steam reforming (MSR) reaction was studied by using both a dense Pd-Ag membrane reactor (MR) and a fixed bed reactor (FBR). Both the FBR and the MR were packed with a new catalyst based on CuOAl2O3ZnOMgO, having an upper temperature limit of around 350 °C. A constant sweep gas flow rate

Micelle-derived catalysts for extended Schulz-Flory

Energy Technology Data Exchange (ETDEWEB)

Abrevaya, H.

1986-01-01

The objective of this program is to develop a synthesis gas conversion catalyst with higher selectivity to liquid fuels, while maintaining catalytic activity and stability at least equivalent relative to state-of-the-art precipitated iron catalysts. During this quarter, the emphasis in the program has been the investigation of the hydrocarbon cutoff hypothesis with supported ruthenium catalysts. An alumina-supported catalyst with smaller than 20[Angstrom] ruthenium particles was tested under conditions of maximal water gas shift activity. During this test more than 90% of the water made in the Fischer-Tropsch synthesis reaction was converted to H[sub 2]. However, the extent of ruthenium metal agglomeration was not reduced. Accordingly, it was not possible to conclude whether hydrocarbon cutoff occurs with smaller than 20[Angstrom] ruthenium particles on [gamma]-alumina. A ruthenium catalyst prepared on Y-type zeolite had 20[Angstrom] or smaller ruthenium particles according to STEM examination and a 15[Angstrom] average ruthenium metal particle size according to EXAFS examination. The ruthenium metal particle size was stable during the test with this catalyst. The hydrocarbon product distribution was Anderson-Schulz-Flory with no cutoff up to a carbon number of 160. A well-dispersed titania-supported ruthenium catalyst is going to be evaluated during the next quarter in order to determine whether hydrocarbon cutoff occurs.

Catalytic Performance for Hydrocarbon Production from Syngas on the Promoted Co-Based Hybrid Catalysts; Influence of Pt Contents

Directory of Open Access Journals (Sweden)

Suk-Hwan Kang

2017-10-01

How to Cite: Kang, S.H., Ryu, J.H., Kim, J.H., Kim, H.S., Yang, H.C., Chung, D.Y. (2017. Catalytic Performance for Hydrocarbon Production from Syngas on the Promoted Co-Based Hybrid Catalysts; Influence of Pt Contents. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (3: 452-459 (doi:10.9767/bcrec.12.3.592.452-459

Alkali resistant Ni-loaded yolk-shell catalysts for direct internal reforming in molten carbonate fuel cells

Science.gov (United States)

Jang, Won-Jun; Hong, Young Jun; Kim, Hak-Min; Shim, Jae-Oh; Roh, Hyun-Seog; Kang, Yun Chan

2017-06-01

A facile and scalable spray pyrolysis process is applied to synthesize multi-shelled Ni-loaded yolk-shell catalysts on various supports (Al2O3, CeO2, ZrO2, and La(OH)3). The prepared catalysts are applied to direct internal reforming (DIR) in a molten carbonate fuel cell (MCFC). Even on exposure to alkali hydroxide vapors, the Ni-loaded yolk-shell catalysts remain highly active for DIR-MCFCs. The Ni@Al2O3 microspheres show the highest conversion (92%) of CH4 and the best stability among the prepared Ni-loaded yolk-shell catalysts. Although the initial CH4 conversion of the Ni@ZrO2 microspheres is higher than that of the Ni@CeO2 microspheres, the Ni@CeO2 microspheres are more stable. The catalytic performance is strongly dependent on the surface area and acidity and also partly dependent on the reducibility. The acidic nature of Al2O3 combined with its high surface area and yolk-shell structure enhances the adsorption of CH4 and resistance against alkali poisoning, resulting in efficient DIR-MCFC reactions.

Recovering low-boiling hydrocarbons, etc

Energy Technology Data Exchange (ETDEWEB)

Pier, M

1934-10-03

A process is described for the recovery of low-boiling hydrocarbons of the nature of benzine through treatment of liquid carbonaceous materials with hydrogen under pressure at raised temperature, suitably in the presence of catalysts. Middle oils (practically saturated with hydrogen) or higher boiling oils at a temperature above 500/sup 0/ (with or without the addition of hydrogen) containing cyclic hydrocarbons not saturated with hydrogen are changed into low boiling hydrocarbons of the nature of benzine. The cracking takes place under strongly hydrogenating conditions (with the use of a strongly active hydrogenating catalyst or high pressure) at temperatures below 500/sup 0/. If necessary, the constituents boiling below 200/sup 0/ can be reconverted into cyclic hydrocarbons partially saturated with hydrogen. (BLM)

Steam reforming of biomass derived oxygenates to hydrogen : Importance of metal-support boundary

NARCIS (Netherlands)

Takanabe, K.; Aika, Ken-ichi; Seshan, Kulathu Iyer; Lefferts, L.

2006-01-01

Steam reforming of acetic acid over Pt/ZrO2 catalysts was studied as a model reaction of steam reforming of biomass derived oxygenates. Pt/ZrO2 catalysts were very active; however, the catalyst deactivated in time by formation of oligomers which block the active sites for steam reforming.

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.

Report on surveys in fiscal 1999 on research and development of the environment harmonizing catalyst technology; 1999 nendo kankyo chowagata shokubai gijutsu no kenkyu kaihatsu chosa hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

This paper reports the surveys in fiscal 1999 on research and development of the environment harmonizing catalyst technology. The discussion subjects taken up included suppression of discharge of carbon dioxide, catalysts used when manufacturing hydrogen and technology thereof, and environment purifying catalysts to decompose harmful substances, and technology thereof. The roles of catalysts and their technologies are expected in reducing the reforming temperatures, achieving energy saving, and reducing decomposition energy. Furthermore, the catalysts are expected of high activity, long life and low cost. Three themes were selected from the emergency and importance points of view. The themes are, in the consumer field, research and development of efficiency improvement in membrane reactors for reforming low-grade hydrocarbons to structure a technology to manufacture hydrogen for small-size portable fuel cells; and in the industrial field, development of hydrogen and carbon product manufacturing technologies with which CO2 generation is suppressed by means of the catalytic decomposition process. In practice, for such discharged harmful substances as dioxins, PCB and volatile organic compounds (VOC), treating them is the urgent environmental problem, and therefore, the fundamental research was taken up for practical application of the second-generation catalysts of the ultra-violet light and visible light responding type. (NEDO)

Activated carbon as catalyst for microwave-assisted wet peroxide oxidation of aromatic hydrocarbons.

Science.gov (United States)

Garcia-Costa, Alicia L; Lopez-Perela, Lucia; Xu, Xiyan; Zazo, Juan A; Rodriguez, Juan J; Casas, Jose A

2018-05-21

This paper addresses the removal of four aromatic hydrocarbons typically found in petrochemical wastewater: benzene (B), toluene (T), o-xylene (X), and naphthalene (N), by microwave-assisted catalytic wet peroxide oxidation (MW-CWPO) using activated carbon (AC) as catalyst. Under the studied conditions, complete pollutant elimination (B, 1.28 mM; T, 1.09 mM; X, 0.94 mM; and N, 0.78 mM) was achieved, with more than 90% TOC removal after only 15-min reaction time, working at 120 °C, pH 0  = 3, AC at 1 g L -1 , and H 2 O 2 at the stoichiometric dose. Furthermore, in the case of toluene, naphthalene, and xylene, the hydroxylation and breakdown of the ring is very rapid and toxic intermediates were not detected. The process follows two steps: (i) pollutant adsorption onto AC followed by (ii) adsorbed compounds oxidation. Thus, MW-CWPO with AC as catalyst appears a promising way for a fast and effective process for B, T, X, and N removal in aqueous phase.

A PROCESS FOR THE CATALYTIC OXIDATION OF HYDROCARBONS

DEFF Research Database (Denmark)

1999-01-01

A process for producing an alcohol from a gaseous hydrocarbon, e.g. a lower alkane such as methane, via oxidative reaction of the hydrocarbon in a concentrated sulfuric acid medium in the presence of a catalyst employs an added catalyst comprising a substance selected from iodine, iodine compounds...

Steam Reforming of Bio-oil Model Compounds

DEFF Research Database (Denmark)

Trane, Rasmus; Jensen, Anker Degn; Dahl, Søren

The steam reforming of bio-oil is a sustainable and renewable route to synthesis gas and hydrogen, where one of the main hurdles is carbon formation on the catalyst.......The steam reforming of bio-oil is a sustainable and renewable route to synthesis gas and hydrogen, where one of the main hurdles is carbon formation on the catalyst....

Hydrogen Production via Steam Reforming of Ethyl Alcohol over Palladium/Indium Oxide Catalyst

Directory of Open Access Journals (Sweden)

Tetsuo Umegaki

2009-01-01

Full Text Available We report the synergetic effect between palladium and indium oxide on hydrogen production in the steam reforming reaction of ethyl alcohol. The palladium/indium oxide catalyst shows higher hydrogen production rate than indium oxide and palladium. Palladium/indium oxide affords ketonization of ethyl alcohol with negligible by-product carbon monoxide, while indium oxide mainly affords dehydration of ethyl alcohol, and palladium affords decomposition of ethyl alcohol with large amount of by-product carbon monoxide. The catalytic feature of palladium/indium oxide can be ascribed to the formation of palladium-indium intermetallic component during the reaction as confirmed by X-ray diffraction and X-ray photoelectron spectroscopic measurements.

The cycle use test of Pt based catalyst for the steam reforming of naphthalene / benzene as model tar compounds of biomass gasification

Energy Technology Data Exchange (ETDEWEB)

Furusawa, Takeshi; Saito, Katsuhiko; Sato, Masahide; Suzuki, Noboru [Utsunomiya Univ. (Japan). Graduate School of Engineering

2010-07-01

Although Pt/Al{sub 2}O{sub 3} catalyst showed high and stable activity (carbon conv. to gas: 90%) for steam reforming of naphthalene/benzene at 1073 K with S/C=3, this catalyst gradually lost its activity at 1023 K with S/C=3 due to deposition of carboneous species. Two kinds of regeneration treatment was conducted to enlongate the life time of Pt/Al{sub 2}O{sub 3} catalyst. Although regeneration treatment completely remove the carboneous species from catalyst, mild oxidation treatment led to decrease activity due to sintering of Pt particles. On the contrary, hydrogen treatment led to maintain activity until 5th cycle test. It was concluded from these obtained results that hydrogen treatment is suitable regeneration method during cycle test in the case of Pt/Al{sub 2}O{sub 3} catalyst. (orig.)

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)

Preparation and characterization of nickel catalysts supported on cerium for obtaining hydrogen from steam reforming of ethanol; Preparacao e caracterizacao de catalisadores de niquel suportados em ceria para obtencao de hidrogenio a partir da reforma a vapor do etanol

Energy Technology Data Exchange (ETDEWEB)

Urbaninho, A.B.; Bergamaschi, V.S.; Ferreira, J.C., E-mail: jcferrei@ipen.br [Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP), São Paulo, SP (Brazil). Centro de Células à Combustível e Hidrogênio

2016-07-01

The Ni/Ce catalysts for were prepared by co- precipitation method with a view to their use in steam reforming of ethanol to produce a hydrogen-rich gas mixture. The catalysts were characterized by scanning electron microscopy; x-ray dispersive Spectroscopy and surface area BET method. This paper proposes to prepare, characterize and test nickel catalyst supported on cerium in order to obtain a material with higher activity and selectivity of the catalyst using the steam reforming reaction of ethanol, by varying the reaction temperature, molar ratio water/ethanol and uptime. The catalytic tests were monitored by chemical analysis of syngas from steam reforming of ethanol using an analysis online by gas Chromatograph in the reactor. (author)

Modeling and simulation of graphene/palladium catalyst reformer for hydrogen generation from waste of IC engine

Science.gov (United States)

Rahman, A.; Aung, K. M.

2018-01-01

A small amount of hydrogen made by on-board reformer is added to the normal intake air and gasoline mixture in the vehicle’s engine could improves overall combustion quality by allowing nearly twice as much air for a given amount of fuel introduced into the combustion chamber. This can be justified based on the calorific value of Hydrogen (H2) 141.9 MJ/kg while the gasoline (C6.4H11.8) is 47MJ/kg. Different weight % of Pd and GO uses for the reformer model and has conducted simulation by COMSOL software. The best result found for the composition of catalyst (palladium 30% and graphene 70%). The study shows that reformer yield hydrogen 23% for the exhaust temperature of 600-900°C and 20% for 80-90°C. Pumping hydrogen may boost the fuel atomization and vaporization at engine idle condition, which could enhances the fuel combustion efficiency. Thus, this innovative technology would be able to save fuel about 12% and reduce the emission about 35%.

Characterization of Coke on a Pt-Re/γ-Al _2 O _3 Re-Forming Catalyst: Experimental and Theoretical Study

International Nuclear Information System (INIS)

Bare, Simon R.; Vila, F. D.; Prabhakar, Sesh; Bradley, William J.

2017-01-01

The characterization of coke on spent catalysts is key to understanding deactivation mechanisms in hydrocarbon transformations. Here, we report the comprehensive characterization (using laser Raman spectroscopy, "1"3C MAS NMR, temperature-programmed oxidation, XPS, and carbon K-edge NEXAFS) of coke on a series of spent Pt-Re re-forming catalysts as a function of time on stream and position in the catalytic bed. Laser Raman spectroscopy is shown to be rather insensitive to the carbon species present, while "1"3C MAS NMR finds that the carbon is present primarily as aromatic carbon. The TPO data are consistent with the coke being present on the alumina support and not to a large extent covering the metallic Pt-Re nanoclusters, but the data do suggest the presence of more than one type of coke present. The carbon K-edge NEXAFS data, however, clearly differentiate the types of coke species present. In the more coked samples the features ascribed to graphite become more pronounced, together with an increase in the aromaticity, as judged by the intensity of the π* peak. With increasing amounts of carbon on the catalyst there is also a concomitant decrease in the σ* C–H peak, indicating that the carbon is becoming less hydrogenated. Furthermore, by using a linear combination of C NEXAFS spectra for n-hexane, benzene, and broadened highly oriented pyrolytic graphite (HOPG), we estimate the compositional change on the coke species, verifying the aliphatic to aromatic conversion. The data indicate that a good model for the deposited coke is that of highly defected, medium-sized rafts with a short-range polycyclic aromatic structure which have a variety of points of contact with the alumina surface, in particular with the O atoms. In agreement with the NMR, there is evidence for the C–O functionality from the presence of a shoulder in the C NEXAFS spectra that is ascribed, as a result of DFT calculations, to a 1s → π* transition of the carbon atoms bound to the

Novel Auto thermal Reforming Process for Pure Hydrogen Production

International Nuclear Information System (INIS)

Chen, Z.; Elnashaie, S.S.E.H.

2004-01-01

Steam reforming of heptane for hydrogen production is investigated in a novel Circulating Fluidized Bed Membrane Reformer-Regenerator system (CFBMRR) utilizing a number of hydrogen and oxygen selective membranes. It is shown that although the amount of carbon deposition is significant, the effect on catalyst deactivation is negligible due to the large solid to gas mass feed ratio and the continuous catalyst regeneration in the system. The combustion of the deposited carbon in the catalyst regenerator supplies the heat needed for the endothermic steam reforming as well as the combustion of flammable gases from the riser reformer. Auto thermal operation is achievable for the entire adiabatic reformer-regenerator system when the exothermic heat generated from the regenerator is sufficient to compensate the endothermic heat consumed in the reformer. Multiplicity of the steady states exists in the range of steam to carbon feed ratio of 1.4442.251 mol/mol. The novel configuration has the potential advantages not only with respect to hydrogen production but also energy minimization

NEW MATERIAL NEEDS FOR HYDROCARBON FUEL PROCESSING: Generating Hydrogen for the PEM Fuel Cell

Science.gov (United States)

Farrauto, R.; Hwang, S.; Shore, L.; Ruettinger, W.; Lampert, J.; Giroux, T.; Liu, Y.; Ilinich, O.

2003-08-01

The hydrogen economy is fast approaching as petroleum reserves are rapidly consumed. The fuel cell promises to deliver clean and efficient power by combining hydrogen and oxygen in a simple electrochemical device that directly converts chemical energy to electrical energy. Hydrogen, the most plentiful element available, can be extracted from water by electrolysis. One can imagine capturing energy from the sun and wind and/or from the depths of the earth to provide the necessary power for electrolysis. Alternative energy sources such as these are the promise for the future, but for now they are not feasible for power needs across the globe. A transitional solution is required to convert certain hydrocarbon fuels to hydrogen. These fuels must be available through existing infrastructures such as the natural gas pipeline. The present review discusses the catalyst and adsorbent technologies under development for the extraction of hydrogen from natural gas to meet the requirements for the proton exchange membrane (PEM) fuel cell. The primary market is for residential applications, where pipeline natural gas will be the source of H2 used to power the home. Other applications including the reforming of methanol for portable power applications such as laptop computers, cellular phones, and personnel digital equipment are also discussed. Processing natural gas containing sulfur requires many materials, for example, adsorbents for desulfurization, and heterogeneous catalysts for reforming (either autothermal or steam reforming) water gas shift, preferential oxidation of CO, and anode tail gas combustion. All these technologies are discussed for natural gas and to a limited extent for reforming methanol.

Production of hydrocarbons of value

Energy Technology Data Exchange (ETDEWEB)

1931-06-16

A process is described for the production of hydrocarbons of great value by treating with heat and pressure carbonaceous materials such as coals, tars, mineral oils, and products of distillation and transformation of these materials, also for the refining with heat and pressure of mixed liquid hydrocarbons by means of hydrogen gas, preferably in the presence of catalysts, consisting in using as the hydrogenating gas that obtained by gasification of combustible solids after partial or complete cleaning at atmospheric or elevated pressures, by means of solid adsorbents, chemical agents or catalysts, or mixtures of these agents, the hydrocarbons being characterized by strong unsaturation, and the presence of oxygen, sulfur compounds, and oxides of nitrogen.

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)

Decentralized production of hydrogen from hydrocarbons with reduced CO2 emission

International Nuclear Information System (INIS)

Nazim Muradov; Franklyn Smith; Cunping Huang; Ali T-Raissi

2006-01-01

Currently, most of the industrial hydrogen production is based on steam methane reforming process that releases significant amount of CO 2 into the atmosphere. CO 2 sequestration is one approach to solving the CO 2 emission problem for large centralized hydrogen plants, but it would be impractical for decentralized H 2 production units. The objective of this paper is to explore new routes to hydrogen production from natural gas without (or drastically reduced) CO 2 emissions. One approach analyzed in this paper is based on thermo-catalytic decomposition (TCD) of hydrocarbons (e.g., methane) to hydrogen gas and elemental carbon. The paper discusses some technological aspects of the TCD process development: (1) thermodynamic analysis of TCD using AspenPlus chemical process simulator, (2) heat input options to the endothermic process, (3) catalyst activity issues, etc. Production of hydrogen and carbon via TCD of methane was experimentally verified using carbon-based catalysts. (authors)

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-07-15

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

Thermodynamic analysis of ethanol/water system in a fuel cell reformer with the Gibbs energy minimization method

International Nuclear Information System (INIS)

Lima da Silva, Aline; De Fraga Malfatti, Celia; Heck, Nestor Cesar

2003-01-01

The use of fuel cells is a promising technology in the conversion of chemical to electrical energy. Due to environmental concerns related to the reduction of atmospheric pollution and greenhouse gases emissions such as CO 2 , NO x and hydrocarbons, there have been many researches about fuel cells using hydrogen as fuel. Hydrogen gas can be produced by several routes; a promising one is the steam reforming of ethanol. This route may become an important industrial process, especially for sugarcane producing countries. Ethanol is renewable energy and presents several advantages over other sources related to natural availability, storage and handling safety. In order to contribute to the understanding of the steam reforming of ethanol inside the reformer, this work displays a detailed thermodynamic analysis of the ethanol/water system, in the temperature range of 500-1200K, considering different H 2 O/ethanol reforming ratios. The equilibrium determinations were done with the help of the Gibbs energy minimization method using the Generalized Reduced Gradient algorithm (GRG). Based on literature data, the species considered in calculations were: H 2 , H 2 O, CO, CO 2 , CH 4 , C 2 H 4 , CH 3 CHO, C 2 H 5 OH (gas phase) and C gr . (graphite phase). The thermodynamic conditions for carbon deposition (probably soot) on catalyst during gas reforming were analyzed, in order to establish temperature ranges and H 2 O/ethanol ratios where carbon precipitation is not thermodynamically feasible. Experimental results from literature show that carbon deposition causes catalyst deactivation during reforming. This deactivation is due to encapsulating carbon that covers active phases on a catalyst substrate, e.g. Ni over Al 2 O 3 . In the present study, a mathematical relationship between Lagrange multipliers and the carbon activity (with reference to the graphite phase) was deduced, unveiling the carbon activity in the reformer atmosphere. From this, it is possible to foreseen if soot

Hydrogen generation from bioethanol reforming: bench-scale unit performance with Cu/Nb2O5 catalyst

International Nuclear Information System (INIS)

Fernandes Machado, N.R.C.; Schmal, M.; Cantao, M.P.

2003-01-01

As an alternative route for hydrogen production, ethanol reforming was studied in a bench-scale unit using a 5%Cu/Nb 2 O 5 catalyst previously selected in a micro reactor. X-Ray Diffraction analysis has shown that this catalyst contains copper oxide in an amorphous form, or in particles smaller than 20 nm, while the Nb 2 O 5 is highly crystalline. Analysis of the calcinated catalyst by X-Ray Photoelectron Spectroscopy revealed that 35% of total copper was on the surface as Cu I (55%) or Cu II (45%). The catalyst presented a low surface area (35 m 2 /g), mainly from meso and macropores, as textural analysis revealed. Temperature Programmed Reduction showed a two-step reduction of Cu II to Cu, at 245 o C and 306 o C. It was also observed the reduction of 6% of Nb 2 O 5 . The reaction unit consisted of an integral reactor with 16 g of catalyst pellets, approximately 3 mm x 5 mm in size. Reaction temperature and feed rate were varied to optimize hydrogen production, with CO 2 as the main byproduct. Reagents (water and ethanol) in stoichiometric proportion were fed into an electric pre-heater and vaporized. An increase on reaction temperature from 300 o C to 400 o C has led to an increase in mean conversion from 17% to 35%. Ethene and ethyl ether were also detected as minor byproducts. (author)

Investigation of the promoting effect of Mn on a Pt/C catalyst for the steam and aqueous phase reforming of glycerol

Energy Technology Data Exchange (ETDEWEB)

Bossola, Filippo; Pereira-Hernández, Xavier Isidro; Evangelisti, Claudio; Wang, Yong; Dal Santo, Vladimiro

2017-05-01

The catalytic performances in steam reforming (SR) and aqueous phase reforming (APR) of glycerol of a bimetallic Pt-Mn catalyst supported on activated carbon are investigated and correlated with the surface properties of the catalyst. Under SR conditions, Mn showed a significant promoting effect over Pt/C, both in terms of hydrogen production rate and conversion, with a higher selectivity toward the glycerol dehydration products. Upon addition of Mn the amount of strong Lewis acid sites increased, promoting the dehydration of glycerol and favoring the CAO over CAC cleavage at expenses of hydrogen selectivity. Conversely, under APR conditions, a slightly higher hydrogen selectivity and only minimal enhancement in hydrogen production were found, while the products selectivity was comparable to Pt/C. Most of Mn leached into the aqueous media, but the remaining (<5% of the fresh parent sample) might be alloyed with Pt and promote the CO desorption from neighbor Pt sites.

Steam reforming of technical bioethanol for hydrogen production

DEFF Research Database (Denmark)

Rass-Hansen, Jeppe; Johansson, Roger; Møller, Martin Hulbek

2008-01-01

Essentially all work on ethanol steam reforming so far has been carried out using simulated bioethanol feedstocks, which means pure ethanol mixed with water. However, technical bioethanol consists of a lot of different components including sugars, which cannot be easily vaporized and steam reformed....... For ethanol steam reforming to be of practical interest, it is important to avoid the energy-intensive purification steps to fuel grade ethanol. Therefore, it is imperative to analyze how technical bioethanol, with the relevant impurities, reacts during the steam reforming process. We show how three different...... bioethanol will result in a faster catalyst deactivation than what is observed when using pure ethanol-water mixtures because of contaminants remaining in the feed. However, the initial activity of the catalysts are not affected by this, hence it is important to not only focus on catalyst activity but rather...

Advanced Catalysis Technologies: Lanthanum Cerium Manganese Hexaaluminate Combustion Catalysts for Flat Plate Reactor for Compact Steam Reformers

Science.gov (United States)

2008-12-01

packed-bed steam reformer reactor using an open-flame or radiant burner as the heat source, the rate of heat transfer is limited by wall film and bed...resistances. Heat transfer can be effectively improved by replacing the burner /packed-bed system with parallel channels containing metal foam...combustion reactor was tested using the hexaaluminate catalyst in pellets and supported on FeCrAlloy metal foam. Both tests burned propane and JP-8

Mixture preparation by cool flames for diesel-reforming technologies

Science.gov (United States)

Hartmann, L.; Lucka, K.; Köhne, H.

The separation of the evaporation from the high-temperature reaction zone is crucial for the reforming process. Unfavorable mixtures of liquid fuels, water and air lead to degradation by local hot spots in the sensitive catalysts and formation of unwanted by-products in the reformer. Furthermore, the evaporator has to work with dynamic changes in the heat transfer, residence times and educt compositions. By using exothermal pre-reactions in the form of cool flames it is possible to realize a complete and residue-free evaporation of liquid hydrocarbon mixtures. The conditions whether cool flames can be stabilised or not is related to the heat release of the pre-reactions in comparison to the heat losses of the system. Examinations were conducted in a flow reactor at atmospheric pressure and changing residence times to investigate the conditions under which stable cool flame operation is possible and auto-ignition or quenching occurs. An energy balance of the evaporator should deliver the values of heat release by cool flames in comparison to the heat losses of the system. The cool flame evaporation is applied in the design of several diesel-reforming processes (thermal and catalytic partial oxidation, autothermal reforming) with different demands in the heat management and operation range (air ratio λ, steam-to-carbon ratio, SCR). The results are discussed at the end of this paper.

New catalysts for selective hydrogenation of diene and acetylene hydrocarbons into olefins

Energy Technology Data Exchange (ETDEWEB)

Frolov, V.M.; Parenago, O.P.; Shuikina, L.P.

1978-12-01

New catalysts for selective hydrogenation of diene and acetylene hydrocarbons into olefins were obtained by reacting aqueous palladium, rhodium, or nickel chloride (0.005-0.05 mole/l.) at 50/sup 0/C, in an argon atmosphere with chelating nitrogen compounds, i.e., o-phenanthroline, ..cap alpha..,..cap alpha..'-dipyridyl, sodium ethylenediaminetetracetate, morpholine, branched polyethylene imines, or amino acids such as glycine, ..cap alpha..-alanine, ..beta..-phenyl-..cap alpha..-alanine, tyrosine, or histidine, and treating the complexes so obtained with sodium borohydride at 1:1-1:5 NaBH/sub 4/-metal ratios, in an aqueous medium. Palladium-based complexes showed the highest activities (20-98Vertical Bar3< conversion) and selectivities (98-100Vertical Bar3<) in heterogeneous hydrogenation of cyclopentadiene, butadiene, 1-hexyne, 1,3-cyclohexadiene, or 1,3-cyclooctadiene at 20/sup 0/-60/sup 0/C and 0.5-15 atm hydrogen, carried out in a kinetic circulation reactor or a metallic autoclave. Thus, a catalytic system based on PdCl/sub 2/ and ..beta..-phenyl-..cap alpha..-alanine converted 98Vertical Bar3< of cyclopentadiene to cyclopentene with 99Vertical Bar3< selectivity. The palladium-based catalyst did not deactivate on the contact with air.

Effect study of the support in nickel and cobalt catalysts for obtaining hydrogen from ethanol steam reforming

International Nuclear Information System (INIS)

Silva, Sirlane Gomes da

2013-01-01

A range of oxide-supported metal catalysts have been investigated for the steam reforming of ethanol for the production of hydrogen and subsequent application in fuel cells. The catalysts were synthesized by the co-precipitation and internal gelification methods using cobalt and nickel as active metals supported on aluminum, zirconium, lanthanum and cerium oxides. After prepared and calcined at 550 Cº the solids were fully characterized by different techniques such as X-rays diffraction(DRX), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy, nitrogen adsorption (B.E.T), temperature-programmed reduction in H2 (TPR-H2) and thermogravimetric analysis. The catalytic tests were performed in a monolithic quartz reactor and submitted to different thermodynamic conditions of steam reforming of ethanol at temperatures varying from 500º C to 800 ºC. The product gas streams from the reactor were analyzed by an on-line gas chromatograph. The cobalt/nickel catalyst supported on a ceria-lanthania mixture (Co 10% / Ni 5% - CeO 2 La 2 O 3 ) showed good catalytic performance in hydrogen selectivity reaching a concentration greater than 65%, when compared to other catalytic systems such as: Co 10% / Ni5% - CeO 2 ; Co 10% / Ni 5% - CeO 2 ZrO 2 ; Co 10% / Ni 5% - ZrO 2 ; Co 10% / Ni 5% - La 2 O 3 ; Co 10% / Ni 5% - CeO 2 La 2 O 3 /K 2% ; Co 10 % / Ni 5% - CeO 2 La 2 O 3 / Na 2% ; Ni 10% / Co 5% - CeO 2 La 2 O 3 ; Co-Al 2 O 3 e Co-Al 2 O 3 CeO 2 . (author)

Nature of hydrocarbon activation in oxidative ammonolysis of propane to acrylonitrile over a gallium-antimony oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Osipova, Z.G.; Sokolovskii, V.D.

1979-03-01

The nature of hydrocarbon activation in oxidative ammonolysis of propane to acrylonitrile over a gallium-antimony oxide catalyst GaSbNiPOx (1:3:1.5:1 atomic ratios of the elements) was studied by comparing the rate of this reaction at 550/sup 0/C and 5Vertical Bar3< by vol propane/6Vertical Bar3< ammonia/18.6Vertical Bar3< oxygen/70.4Vertical Bar3< helium reactant mixture with that of isobutane ammoxidation to methacrylonitrile under the same conditions, at low (Vertical Bar3; 20Vertical Bar3<) conversions that prevent secondary oxidation of the products. Both the over-all hydrocarbon conversion rate and that of nitrile formation were higher for propane, suggesting that the reactions proceed via the respective carbanions (probably primary carbanions), rather than carbocations or uncharged radicals.

Hydrogen production by steam reforming methanol for polymer electrolyte fuel cells

International Nuclear Information System (INIS)

Amphlett, J.C.; Creber, K.A.M.; Davis, J.M.; Mann, R.F.; Peppley, B.A.; Stokes, D.M.

1993-01-01

Catalytic steam reforming of methanol has been studied as a means of generating hydrogen for a polymer electrolyte membrane fuel cell. A semi-empirical model of the kinetics of the catalytic steam reforming of methanol over Cu O/Zn O/Al 2 O 3 catalyst has been developed. This model is able to predict the performance of the reformer with respect to the various parameters important in developing an integrated reformer-polymer fuel cell system. A set of sample calculations of reformer temperature and CO production are given. The impact of the performance of the reformer catalyst on the design of the overall fuel cell power system is discussed. The selectivity of the catalyst to minimize CO content in the fuel gas is shown to be more critical than was previously believed. 4 figs., 4 tabs., 11 refs

Zeolitic catalytic conversion of alcohols to hydrocarbons

Science.gov (United States)

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2018-04-10

A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

Zeolitic catalytic conversion of alochols to hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2017-01-03

A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

Process of distilling heavy hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1929-12-03

This invention has for its object the distillation of heavy liquid hydrocarbons for the purpose of obtaining lighter hydrocarbons stable and immediately salable for fuels in combustion motors. The process is distinguished by the fact that the heavy hydrocarbon is distilled by means of heating to a temperature in keeping with the nature of the material to be treated up to 350/sup 0/C under pressure or without pressure the distillation being carried out on catalysts containing successively nickel, copper, and iron (3 parts of nickel, 1 part of copper, and 1 part of iron), the vapors produced by this distillation being exposed in turn to the action of catalysts of the same nature and in the same proportion.

Developing an energy efficient steam reforming process to produce hydrogen from sulfur-containing fuels

Science.gov (United States)

Simson, Amanda

Hydrogen powered fuel cells have the potential to produce electricity with higher efficiency and lower emissions than conventional combustion technology. In order to realize the benefits of a hydrogen fuel cell an efficient method to produce hydrogen is needed. Currently, over 90% of hydrogen is produced from the steam reforming of natural gas. However, for many applications including fuel cell vehicles, the use of a liquid fuel rather than natural gas is desirable. This work investigates the feasibility of producing hydrogen efficiently by steam reforming E85 (85% ethanol/15% gasoline), a commercially available sulfur-containing transportation fuel. A Rh-Pt/SiO2-ZrO2 catalyst has demonstrated good activity for the E85 steam reforming reaction. An industrial steam reforming process is often run less efficiently, with more water and at higher temperatures, in order to prevent catalyst deactivation. Therefore, it is desirable to develop a process that can operate without catalyst deactivation at more energy efficient conditions. In this study, the steam reforming of a sulfur-containing fuel (E85) was studied at near stoichiometric steam/carbon ratios and at 650C, conditions at which catalyst deactivation is normally measured. At these conditions the catalyst was found to be stable steam reforming a sulfur-free E85. However, the addition of low concentrations of sulfur significantly deactivated the catalyst. The presence of sulfur in the fuel caused catalyst deactivation by promoting ethylene which generates surface carbon species (coke) that mask catalytic sites. The amount of coke increased during time on stream and became increasingly graphitic. However, the deactivation due to both sulfur adsorption and coke formation was reversible with air treatment at 650°C. However, regenerations were found to reduce the catalyst life. Air regenerations produce exotherms on the catalyst surface that cause structural changes to the catalyst. During regenerations the

Cobalt catalysts, and use thereof for the conversion of methanol and for fischer-tropsch synthesis, to produce hydrocarbons

International Nuclear Information System (INIS)

Mauldin, C.H.; Davis, S.M.; Arcuri, K.B.

1988-01-01

This patent describes a process useful for the conversion of methanol to hydrocarbons which comprises contacting the methanol at reaction conditions with a catalyst which comprises from about 2 percent to about 25 percent cobalt, based on the weight of the catalyst composition, composited with titania, or a titania-containing support, to which is added a zirconium, hafnium, cerium, or uranium promoter, the weight ratio of the zirconium, hafnium, cerium, or uranium metal:cobalt being greater than about 0.010:1; the reaction conditions being defined within ranges as follows: Methanol:H/sub 2/ ratio: greater than about 4:1, Space Velocities, Hr/sup -1/:about 0.1 to 10, Temperatures, 0 C.:about 150 to 350, Methanol Partial Pressure, psia: about 100 to 1000

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-07-15

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

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

Science.gov (United States)

Pan, Wei

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

Novel Fischer-Tropsch catalysts. [DOE patent

Science.gov (United States)

Vollhardt, K.P.C.; Perkins, P.

Novel compounds are described which are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO + H/sub 2/ to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

The effect of supercritical isobutane regeneration on the nature of hydrocarbons deposited on a USY zeolite catalyst utilized for isobutane/butene alkylation

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; Lucia M. Petkovic

2004-11-01

The chemical nature of hydrocarbons remaining on an ultrastable Y-zeolite (USY) utilized for liquid phase isobutane/butene alkylation reaction at 333 K and 1.1x107 Pa before and after supercritical isobutane regeneration (SFR) at 453 K and 1.1x107 Pa are presented. Catalyst samples were deactivated to different levels by running the alkylation reaction for different times on stream (TOS) and regenerated under flowing supercritical isobutane for 60 min. Nitrogen physisorption, temperature-programmed oxidation (TPO), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and ultraviolet-visible (UV-Vis) spectroscopy measurements suggested that the SFR process was effective in recovering catalyst surface area and micropore volume and that most coke precursors were removed from samples regenerated after short TOS, when the level of activity for trimethylpentanes (TMP) production was high. Samples that were allowed to react for longer TOS contained unsaturated hydrocarbons that, instead of being extracted by the supercritical fluid, dehydrogenated during the SFR process to produce more condensed species.

Catalyst for the use in the hydrotreatment of a heavy hydrocarbon oil, process to its preparation and process to its use

Energy Technology Data Exchange (ETDEWEB)

Shiroto, Y; Higashi, T; Ono, T

1981-10-01

A catalyst with an improved surface activity and a maintained selectivity is used in the decomposition of asphaltenes and the removal of heavy metals from a heavy hydrocarbon oil by hydrotreatment. The catalyst carrier consists of a calcined combination of a mixture from a clay mineral with double chain structure and at least one oxide-forming substance with a metal from the groups II A, III A, IV A or IV B of the periodic system. The catalytic metal component is selected from the groups V B, VI B, VIII or I B of the periodic system.

A comparison of Rh/CeO2/SiO2 catalysts with steam reforming catalysts, dolomite and inert materials as bed materials in low throughput fluidized bed gasification systems

International Nuclear Information System (INIS)

Asadullah, Mohammad; Miyazawa, Tomohisa; Ito, Shin-ichi; Kunimori, Kimio; Koyama, Shuntarou; Tomishige, Keiichi

2004-01-01

The gasification of cedar wood in the presence of Rh/CeO 2 /SiO 2 has been conducted in the laboratory scale fluidized bed reactor using air as a gasifying agent at low temperatures (823-973 K) in order to produce high-quality fuel gas for gas turbine for power generation. The performance of the Rh/CeO 2 /SiO 2 catalyst has been compared with conventional catalysts such as commercial steam reforming catalyst G-91, dolomite and noncatalyst systems by measurements of the cold gas efficiency, tar concentration, carbon conversion to gas and gas composition. The tar concentration was completely negligible in the Rh/CeO 2 /SiO 2 -catalyzed product gas whereas it was about 30, 113, and 139 g/m 3 in G-91, dolomite and noncatalyzed product gas, respectively. Since the carbon conversion to useful gas such as CO, H 2 , and CH 4 are much higher on Rh/CeO 2 /SiO 2 catalyst than others at 873 K, the cold gas efficiency is much higher (71%) in this case than others. The hydrogen content in the product gas is much higher (>24 vol%) than the specified level (>10 vol%) for efficient combustion in the gas turbine engine. The char and coke formation is also very low on Rh/CeO 2 /SiO 2 catalyst than on the conventional catalysts. Although the catalyst surface area was slightly decreased after using the same catalyst in at least 20 experiments, the deactivation problem was not severe

Hydrogen production by biomass steam gasification in fluidized bed reactor with Co catalyst

International Nuclear Information System (INIS)

Kazuhiko Tasaka; Atsushi Tsutsumi; Takeshi Furusawa

2006-01-01

The catalytic performances of Co/MgO catalysts were investigated in steam gasification of cellulose and steam reforming of tar derived from cellulose gasification. For steam reforming of cellulose tar in a secondary fixed bed reactor, 12 wt.% Co/MgO catalyst attained more than 80% of tar reduction. The amount of produced H 2 and CO 2 increased with the presence of catalyst, and kept same level during 2 hr at 873 K. It is indicated that steam reforming of cellulose tar proceeds sufficiently over Co/MgO catalyst. For steam gasification of cellulose in a fluidized bed reactor, it was found that tar reduction increases with Co loading amount and 36 wt.% Co/MgO catalyst showed 84% of tar reduction. The amounts of produced gas kept for 2 hr indicating that 36 wt.% Co/MgO catalyst is stable during the reaction. It was concluded that these Co catalysts are promising systems for the steam gasification of cellulose and steam reforming of cellulose tar. (authors)

Poly-dimethylsiloxane (PDMS) based micro-reactors for steam reforming of methanol

Energy Technology Data Exchange (ETDEWEB)

Ha, Ji Won; Kundu, Arunabha; Jang, Jae Hyuk

2010-11-15

A miniaturized methanol steam reformer with a serpentine type of micro-channels was developed based on poly-dimethylsiloxane (PDMS) material. This way of fabricating micro-hydrogen generator is very simple and inexpensive. The volume of a PDMS micro-reformer is less than 10 cm{sup 3}. The catalyst used was a commercial Cu/ZnO/Al{sub 2}O{sub 3} reforming catalyst from Johnson Matthey. The Cu/ZnO/Al{sub 2}O{sub 3} reforming catalyst particles of mean diameter 50-70 {mu}m was packed into the micro-channels by injecting water based suspension of catalyst particles at the inlet point. The miniaturized PDMS micro-reformer was operated successfully in the operating temperatures of 180-240 C and 15%-75% molar methanol conversion was achieved in this temperature range for WHSV of 2.1-4.2 h{sup -1}. It was not possible to operate the micro-reformer made by pure PDMS at temperature beyond 240 C. Hybrid type of micro-reformer was fabricated by mixing PDMS and silica powder which allowed the operating temperature around 300 C. The complete conversion (99.5%) of methanol was achieved at 280 C in this case. The maximum reformate gas flow rate was 30 ml/min which can produce 1 W power at 0.6 V assuming hydrogen utilization of 60%. (author)

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.

FEEDSTOCK-FLEXIBLE REFORMER SYSTEM (FFRS) FOR SOLID OXIDE FUEL CELL (SOFC)- QUALITY SYNGAS

Energy Technology Data Exchange (ETDEWEB)

Jezierski, Kelly; Tadd, Andrew; Schwank, Johannes; Kibler, Roland; McLean, David; Samineni, Mahesh; Smith, Ryan; Parvathikar, Sameer; Mayne, Joe; Westrich, Tom; Mader, Jerry; Faubert, F. Michael

2010-07-30

The U.S. Department of Energy National Energy Technology Laboratory funded this research collaboration effort between NextEnergy and the University of Michigan, who successfully designed, built, and tested a reformer system, which produced highquality syngas for use in SOFC and other applications, and a novel reactor system, which allowed for facile illumination of photocatalysts. Carbon and raw biomass gasification, sulfur tolerance of non-Platinum Group Metals (PGM) based (Ni/CeZrO2) reforming catalysts, photocatalysis reactions based on TiO2, and mild pyrolysis of biomass in ionic liquids (ILs) were investigated at low and medium temperatures (primarily 450 to 850 C) in an attempt to retain some structural value of the starting biomass. Despite a wide range of processes and feedstock composition, a literature survey showed that, gasifier products had narrow variation in composition, a restriction used to develop operating schemes for syngas cleanup. Three distinct reaction conditions were investigated: equilibrium, autothermal reforming of hydrocarbons, and the addition of O2 and steam to match the final (C/H/O) composition. Initial results showed rapid and significant deactivation of Ni/CeZrO2 catalysts upon introduction of thiophene, but both stable and unstable performance in the presence of sulfur were obtained. The key linkage appeared to be the hydrodesulfurization activity of the Ni reforming catalysts. For feed stoichiometries where high H2 production was thermodynamically favored, stable, albeit lower, H2 and CO production were obtained; but lower thermodynamic H2 concentrations resulted in continued catalyst deactivation and eventual poisoning. High H2 levels resulted in thiophene converting to H2S and S surface desorption, leading to stable performance; low H2 levels resulted in unconverted S and loss in H2 and CO production, as well as loss in thiophene conversion. Bimetallic catalysts did not outperform Ni-only catalysts, and small Ni particles were

Steam Reforming of Ethylene Glycol over Ni/Al2O3 Catalysts: Effect of the Preparation Method and Reduction Temperature

International Nuclear Information System (INIS)

Choi, Dong Hyuck; Park, Jung Eun; Park, Eun Duck

2015-01-01

The effect of preparation method on the catalytic activities of the Ni/Al 2 O 3 catalysts on steam reforming of ethylene glycol was investigated. The catalysts were prepared with various preparation methods such as an incipient wetness impregnation, wet impregnation, and coprecipitation method. In the case of coprecipitation method, various precipitants such as KOH, K 2 CO 3 , and NH 4 OH were compared. The prepared catalysts were characterized by using N 2 physisorption, inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, temperature programmed reduction, pulsed H 2 chemisorption, temperature-programmed oxidation, scanning electron microscopy, and thermogravimetric analysis. Among the catalysts reduced at 773 K, the Ni/Al 2 O 3 catalyst prepared by a coprecipitation with KOH or K 2 CO 3 as precipitants showed the best catalytic performance. The preparation method affected the particle size of Ni, reducibility of nickel oxides, catalytic performance (activity and stability), and types of coke formed during the reaction. The Ni/Al 2 O 3 catalyst prepared by a coprecipitation with KOH showed the increasing catalytic activity with an increase in the reduction temperature from 773 to 1173 K because of an increase in the reduction degree of Ni oxide species even though the particle size of Ni increased with increasing reduction temperature

Hydrogen production from bio-fuels using precious metal catalysts

Science.gov (United States)

Pasel, Joachim; Wohlrab, Sebastian; Rotov, Mikhail; Löhken, Katrin; Peters, Ralf; Stolten, Detlef

2017-11-01

Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3) and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

Experimental, kinetic and numerical modeling of hydrogen production by catalytic reforming of crude ethanol over a commercial catalyst in packed bed tubular reactor and packed bed membrane reactor

International Nuclear Information System (INIS)

Aboudheir, Ahmed; Akande, Abayomi; Idem, Raphael

2006-01-01

The demand for hydrogen energy has increased tremendously in recent years essentially because of the increase in the word energy consumption as well as recent developments in fuel cell technologies. The energy information administration has projected that world energy consumption will increase by 59% over the next two decades, from 1999 to 2020, in which the largest share is still dominated by fossil fuels (oil, natural gas and coal). Carbon dioxide (CO 2 ) emissions resulting from the combustion of these fossil fuels currently are estimated to account for three-fourth of human-caused CO 2 emissions worldwide. Greenhouse gas emission, including CO 2 , should be limited, as recommended at the Kyoto Conference, Japan, in December 1997. In this regard, hydrogen (H 2 ) has a significant future potential as an alternative fuel that can solve the problems of CO 2 emissions as well as the emissions of other air contaminants. One of the techniques to produce hydrogen is by reforming of hydrocarbons or biomass. Crude ethanol (a form of biomass, which essentially is fermentation broth) is easy to produce, is free of sulphur, has low toxicity, and is also safe to handle, transport and store. In addition, crude ethanol consists of oxygenated hydrocarbons, such as ethanol, lactic acid, glycerol, and maltose. These oxygenated hydrocarbons can be reformed completely to H 2 and CO 2 , the latter of which could be separated from H 2 by membrane technology. This provides for CO 2 capture for eventual storage or destruction. In the case of using crude ethanol, this will result in negative CO 2 , emissions. In this paper, we conducted experimental work on production of hydrogen by the catalytic reforming of crude ethanol over a commercial promoted Ni-based catalyst in a packed bed tubular reactor as well as a packed bed membrane reactor. As well, a rigorous numerical model was developed to simulate this process in both the catalytic packed bed tubular reactor and packed bed membrane

Catalysts with Cu base supported in mixed oxides to generate H2: reformed of methanol in oxidant atmosphere

International Nuclear Information System (INIS)

Aguila M, M.M.; Perez H, R.; Rodriguez L, V.

2006-01-01

In this work, the characterization of Cu supported in CeO 2 -ZrO 2 , for to generate H 2 starting from the one reformed of methanol with water vapor and oxygen is presented. The sol-gel technique and classic impregnation for the obtaining of the supports and catalysts respectively were used. The materials were characterized by XRD, SEM, adsorption- desorption of N 2 and TPR. The catalytic materials presented crystalline phases associated with the zircon (tetragonal and monoclinic phase) and the ceria (cubic phase) depending on the CeO 2 /ZrO 2 relationship. The morphology of the catalysts was analyzed by SEM being observed semispheric particles for the rich materials in ZrO 2 and added planars in the rich materials in CeO 2 . The ceria addition to the zircon favors the specific area of the mixed oxides CeO 2 -ZrO 2 and it promotes the reducibility of the copper oxide at low temperatures. The rich catalysts in ceria also showed high activity in the methanol transformation and bigger selectivity toward the production of H 2 . This result is associated with the presence of copper species that decrease to low temperature present in the rich catalysts in ceria and that they are not present in the rich catalysts in zircon. (Author)

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)

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)

Oxidative-reforming of model biogas over NiO/Al{sub 2}O{sub 3} catalysts: The influence of the variation of support synthesis conditions

Energy Technology Data Exchange (ETDEWEB)

Asencios, Yvan J.O., E-mail: yvan.jesus@unifesp.br [Departamento de Ciências do Mar, Universidade Federal de São Paulo, Av. Alm. Saldanha da Gama, 89, Ponta da Praia, CEP: 11030-400, Santos-SP (Brazil); Elias, Kariny F.M. [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil); Assaf, Elisabete M., E-mail: eassaf@iqsc.usp.br [Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense, 400, 13560-970, São Carlos-SP (Brazil)

2014-10-30

Graphical abstract: - Highlights: • Precipitation pH and ageing T °C of Al{sub 2}O{sub 3} influenced the performance of Ni/Al{sub 2}O{sub 3}. • Ni catalysts supported on Al{sub 2}O{sub 3} obtained at pH 7 recorded high conversion values. • Catalysts supported on Al{sub 2}O{sub 3} obtained at pH 7 and 80 °C are promissory for reforming of biogas. • Catalysts supported on Al{sub 2}O{sub 3} obtained at pH 6 deactivated readily during reaction. - Abstract: In this study, nickel catalysts (20 wt%) supported on γ-Al{sub 2}O{sub 3} were prepared by the impregnation method. The γ-Al{sub 2}O{sub 3}, was synthesized by precipitation of bayerite gel obtained from aluminum scrap. The synthetic conditions of the bayerite gel varied as follows: precipitation pH ranging from 6 to 7; ageing temperature ranging from 25 to 80 °C, the calcination temperature for all samples was 500 °C. The catalysts and the supports were analyzed by temperature programmed reduction (H{sub 2}-TPR), X-ray diffraction (XRD), physisorption of N{sub 2} (BET), X-ray absorption near-edge structure (XANES) and scanning electron microscopy (SEM). Isopropanol decomposition reactions over the catalysts were carried out to evaluate their acidity. SEM images of the spent catalysts showed that the morphology of the carbon formed during the reaction is of the filamentous type. The TPR analysis of the catalysts showed the presence of NiO species weakly interacted with the support as well as stoichiometric and non-stoichiometric nickel aluminate, the reduction of these species was also observed by XANES analysis. XRD analysis of the fresh catalyst showed peaks assigned to NiO, NiAl{sub 2}O{sub 4} and γ-Al{sub 2}O{sub 3}. The best catalysts (samples NiAl7-25 and NiAl7-80) synthesized in this report showed high stability and high conversion values (CH{sub 4} (70%) and CO{sub 2} (78%)). These catalysts showed better performance than the catalyst supported on commercial γ-Al{sub 2}O{sub 3}, which showed a

Optimization of the reaction parameters of heavy naphtha reforming process using Pt-Re/Al2O3 catalyst system

Directory of Open Access Journals (Sweden)

Hussien A. Elsayed

2017-12-01

Full Text Available One of the most significant procedures in oil refineries is naphtha catalytic reforming unit in which high octane gasoline is gained. Normally, in oil refineries, flow instability in the composition of feedstock can affect the product quality. The aim of the present work was focused on modifications of the final product flow rate and product’s octane number with respect to the modifications of the feedstock composition. The main three reforming reactions investigated, namely; dehydrogenation, dehydrocyclization, and hydrocracking were conducted employing silica supported bimetallic (Pt-Re patented catalyst. Optimization of the catalytic process reaction conditions, i.e.; temperature, hydrogen pressure and liquid hourly space velocity (LHSV was carried out with regard to conversion and selectivity. The optimization results indicated that heavy naphtha component conversion (paraffin’s and naphthenes increases with an increasing in reaction temperature and pressure while decreases with an increase in LHSV. The kinetic study of catalytic reforming reactions reported helped establishing the reaction model explicitly.

Enhancement of alkylation catalysts for improved supercritical fluid regeneration

Science.gov (United States)

Ginosar, Daniel M.; Petkovic, Lucia M.

2010-12-28

A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

Science.gov (United States)

Zhang, Xinghua; Zhang, Qi; Wang, Tiejun; Ma, Longlong; Yu, Yuxiao; Chen, Lungang

2013-04-01

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hydrogen production from bio-fuels using precious metal catalysts

Directory of Open Access Journals (Sweden)

Pasel Joachim

2017-01-01

Full Text Available Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3 and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

Design of bimetal catalysts Pt-Ni/CeO_2-1D for generation of H_2 by the reforming reaction of methanol

International Nuclear Information System (INIS)

Sarmiento F, I.

2016-01-01

CeO_2 nano rods were synthesized by hydrothermal method and were used as support for preparing catalysts bimetallic Pt Ni / CeO_2-1D. The catalysts were prepared by classical impregnation by the conventional wet method. The prepared catalysts are Pt (0.5 %) - Ni (5 %) / CeO_2 and Pt (0.5 %) - Ni (15 %) / CeO_2, which were characterized by different physico-chemical techniques: Bet, Sem, TPR and XRD, that were evaluated in the Auto thermal Steam reforming of Methanol for H_2 production. The Bet surface area results, show that the surface area of the catalysts decreases as the nominal load of Ni in the catalyst, increases. Sem shows, that the catalyst support (CeO_2-1D) and the bimetallic catalysts are conformed by nano rods. By XRD were identified the crystalline phases present, in the catalytic material: cerianite distinctive phase of cerium oxide and metallic Ni; however it was not possible to observe diffraction peaks of Platinum using this technique. The temperature-programmed reduction (TPR) analysis allowed to obtain the reduction profiles, of the different species present on the catalysts. The catalytic activity tests carried out, showed that the catalysts total 100% methanol conversion is achieved at 300 degrees Celsius, making them excellent, to be used in reactions at low temperature conditions. Selectivity towards H_2, is very similar in both catalysts, and it reaches a 50% yield per mole of methanol fed stoichiometrically. (Author)

Preparing valuable hydrocarbons by hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Pier, M

1930-08-22

A process is described for the preparation of valuable hydrocarbons by treatment of carbonaceous materials, like coal, tars, minerals oils, and their distillation and conversion products, and for refining of liquid hydrocarbon mixture obtained at raised temperature and under pressure, preferably in the presence of catalysts, by the use of hydrogen-containing gases, purified and obtained by distilling solid combustibles, characterized by the purification of the hydrogen-containing gases being accomplished for the purpose of practically complete removal of the oxygen by heating at ordinary or higher pressure in the presence of a catalyst containing silver and oxides of metals of group VI of the periodic system.

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.

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

Chemical deactivation of Ag/Al2O3 by sulphur for the selective reduction of NOx using hydrocarbons

International Nuclear Information System (INIS)

Houel, Valerie; Millington, Paul; Pollington, Stephen; Poulston, Stephen; Rajaram, Raj R.; Tsolakis, Athanasios

2006-01-01

The hydrocarbon-SCR activity of Ag/Al 2 O 3 catalysts is severely deactivated after low temperature (350 o C) sulphur ageing in the form of SO 2 exposure. Catalysts aged with SO 2 , NO and hydrocarbon present accumulate a significantly larger amount of SO 4 2- than those aged in the presence of only O 2 , H 2 O and SO 2 when exposed to an equivalent amount of S. Following sulphation of the catalyst most of the sulphur can be removed by a high temperature (600 o C) treatment in the reaction gas. Regeneration in the absence of hydrocarbon is ineffective. The hydrocarbon-SCR activity of the sulphated catalyst using model hydrocarbons such as n-C 8 H 18 can be restored after a high temperature pre-treatment in the reaction gases. However this desulphation process fails to regenerate the hydrocarbon-SCR activity when diesel fuel is used in the activity test. TPR studies show that a major fraction of the sulphur species present in the catalyst is removed by such pre-treatment, but the slight residual amount of sulphur is sufficient to inhibit the activation of the diesel fuel on the Ag catalyst. The nature of the hydrocarbon species present for the hydrocarbon-SCR reaction and during the regeneration strongly influences the activity. In general aromatics such as C 7 H 8 are less effective for reducing NO x and regenerating the sulphated catalyst. (author)

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Modification the Oxalic Co-precipitation Method on a Novel Catalyst Cu/Zn/Al2O3/Cr2O3 for Autothermal Reforming Reaction of Methanol

Directory of Open Access Journals (Sweden)

Cheng- Hsin Kuo

2013-12-01

Full Text Available This study addresses the catalytic performance of Cu/ZnO/Al2O3/Cr2O3 in low-temperature of autothermal reforming (ATR reaction. Various operating conditions were used to decide the optimum reaction conditions: type of promoter (ZrO2, CeO2, and Cr2O3, precipitation temperature, precipitation pH, operation temperature, molar ratio of O2/CH3OH (O/C, and weight hourly space velocity (WHSV. The catalysts were prepared using the oxalic coprecipitation method. Characterization of the catalyst was conducted using a porosity analyzer, XRD, and SEM. The methanol conversion and volumetric percentage of hydrogen using the best catalyst (Cu/ZnO/Al2O3/Cr2O3 exceeded 93% and 43%, respectively. A catalyst prepared by precipitation at -5 oC and at pH of 1 converted methanol to 40% H2 and less than 3000 ppm CO at reaction temperature of 200 oC. The size and dispersion of copper and the degradation rate and turnover frequency of the catalyst was also calculated. Deactivation of the Cu catalyst at a reaction temperature of 200 oC occurred after 30 h. © 2013 BCREC UNDIP. All rights reservedReceived: 8th May 2013; Revised: 10th August 2013; Accepted: 18th August 2013[How to Cite: Cheng, H.K., Lesmana, D., Wu, H.S. (2013. Modification the Oxalic Co-precipitation Method on a Novel Catalyst Cu/Zn/Al2O3/Cr2O3 for Autothermal Reforming Reaction of Methanol. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 110-124. (doi:10.9767/bcrec.8.2.4844.110-124][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4844.110-124

Simulation of the Dynamics of Isothermal Growth of Single-Layer Graphene on a Copper Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

Science.gov (United States)

Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

2018-01-01

A new kinetic model of isothermal growth of single-layer graphene on a copper catalyst as a result of the chemical vapor deposition of hydrocarbons on it at a low pressure has been developed on the basis of in situ measurements of the growth of graphene in the process of its synthesis. This model defines the synthesis of graphene with regard for the chemisorption and catalytic decomposition of ethylene on the surface of a copper catalyst, the diffusion of carbon atoms in the radial direction to the nucleation centers within the thin melted near-surface copper layer, and the nucleation and autocatalytic growth of graphene domains. It is shown that the time dependence of the rate of growth of a graphene domain has a characteristic asymmetrical bell-like shape. The dependences of the surface area and size of a graphene domain and the rate of its growth on the time at different synthesis temperatures and ethylene concentrations have been obtained. Time characteristics of the growth of graphene domains depending on the parameters of their synthesis were calculated. The results obtained can be used for determining optimum regimes of synthesis of graphene in the process of chemical vapor deposition of hydrocarbons on different catalysts with a low solubility of carbon.

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.

Liquid-Phase Electrical Discharges: Fundamental Mechanisms and Applications

Science.gov (United States)

Franclemont, Joshua

The increased demand in alternative energy in recent decades has generated significant interest in cleaner fuel sources including hydrogen and syngas (hydrogen and carbon monoxide). Hydrogen and syngas are both primarily produced through the steam reforming of hydrocarbons, specifically natural gas. Although other processes are known, the cheapest source of these fuels is currently through the heating of natural gas in the presence of steam and a catalyst. However, due to the emissions associated with the steam reforming of natural gas and the lack of low cost, efficient, and reliable onboard hydrogen storage technologies for fuel cell powered vehicles, attention has been focused on plasma-assisted reforming of hydrocarbons. Plasma processes can be implemented onboard and are able to directly reform liquid hydrocarbons and alcohols without external heating or catalysts. In addition to hydrogen and syngas, the plasma-assisted reforming of hydrocarbons and alcohols offers other desirable products such as C2 gases (ethane, ethylene, and acetylene), methanol and ethanol. The primary goal of this study is to investigate the fundamental chemical reactions occurring during plasma-assisted reforming of liquid hydrocarbons and alcohols using streamer-like pulsed electrical discharges. Due to the relatively unexplored field of chemical reactions in liquid plasmas, the focus of this study is on elucidating chemical pathways responsible for the formation of hydrogen, syngas, and other products during the direct reforming of liquid methanol, glycerol, and pentane as model species.

Engelhard and IFP/Procatalyse set up worldwide catalysts venture

International Nuclear Information System (INIS)

Hunter, D.

1992-01-01

The new joint venture between Engelhard (Iselin, N) and Procatalyse (Paris), jointly owned by process licenser Institut Francais de Petrole (IFP; Rueil Malmaison, France) and Rhone-Poulenc (RP; Paris), marks the latest episode in the worldwide catalyst industry's restructuring. The operation will combine Engelhard's catalyst line, apart from its fluid catalytic cracking (FCC) and emission catalysts, with Procatalyse's offering. To be launched at the beginning of 1993, the venture will have annual sales of about $75 million. Reforming catalysts will be the biggest part of the venture's lineup at the outset, making it number three in the US, behind UOP - which dominates the sector - and Criterion. IFP is starting to establish a presence in North America with its reforming technology. But flat gasoline demand and reductions on aromatics in gasoline limit requirements for new reforming units, comments one competitor. Although lower sulfur specifications are putting some new demand into the hydrodesulfurization (HDS) catalyst market, both partners play down their prospects. The sector, whose leaders are Akzo and Crtierion, is continuing to suffer from severe overcapacity. Procatalyse's HDS business is mainly linked to IFP licensees, while Engelhard is due to mothball its Salt Lake City HDS catalyst plant by year-end, transferring output to Elyria

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)

Auxiliary reactor for a hydrocarbon reforming system

Science.gov (United States)

Clawson, Lawrence G.; Dorson, Matthew H.; Mitchell, William L.; Nowicki, Brian J.; Bentley, Jeffrey M.; Davis, Robert; Rumsey, Jennifer W.

2006-01-17

An auxiliary reactor for use with a reformer reactor having at least one reaction zone, and including a burner for burning fuel and creating a heated auxiliary reactor gas stream, and heat exchanger for transferring heat from auxiliary reactor gas stream and heat transfer medium, preferably two-phase water, to reformer reaction zone. Auxiliary reactor may include first cylindrical wall defining a chamber for burning fuel and creating a heated auxiliary reactor gas stream, the chamber having an inlet end, an outlet end, a second cylindrical wall surrounding first wall and a second annular chamber there between. The reactor being configured so heated auxiliary reactor gas flows out the outlet end and into and through second annular chamber and conduit which is disposed in second annular chamber, the conduit adapted to carry heat transfer medium and being connectable to reformer reaction zone for additional heat exchange.

Development of GREET Catalyst Module

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States); Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States); Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States)

2015-09-01

In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al₂O3, and Pt/ γ-Al₂O₃) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

Hydrous pyrolysis/oxidation process for in situ destruction of chlorinated hydrocarbon and fuel hydrocarbon contaminants in water and soil

Science.gov (United States)

Knauss, Kevin G.; Copenhaver, Sally C.; Aines, Roger D.

2000-01-01

In situ hydrous pyrolysis/oxidation process is useful for in situ degradation of hydrocarbon water and soil contaminants. Fuel hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, petroleum distillates and other organic contaminants present in the soil and water are degraded by the process involving hydrous pyrolysis/oxidation into non-toxic products of the degradation. The process uses heat which is distributed through soils and water, optionally combined with oxygen and/or hydrocarbon degradation catalysts, and is particularly useful for remediation of solvent, fuel or other industrially contaminated sites.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-15

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

A Novel Slurry-Based Biomass Reforming Process Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Emerson, Sean C. [United Technologies Research Center, East Hartford, CT (United States); Davis, Timothy D. [United Technologies Research Center, East Hartford, CT (United States); Peles, A. [United Technologies Research Center, East Hartford, CT (United States); She, Ying [United Technologies Research Center, East Hartford, CT (United States); Sheffel, Joshua [United Technologies Research Center, East Hartford, CT (United States); Willigan, Rhonda R. [United Technologies Research Center, East Hartford, CT (United States); Vanderspurt, Thomas H. [United Technologies Research Center, East Hartford, CT (United States); Zhu, Tianli [United Technologies Research Center, East Hartford, CT (United States)

2011-09-30

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

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)

The development of isomerization catalysts for production of high-octane products

Energy Technology Data Exchange (ETDEWEB)

Pedrosa, A.M. Garrido; Melo, D.M.A.; Araujo, A.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Quimica; Souza, M.J.B.; Silva, A.O.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Engenharia Quimica

2004-07-01

In current petroleum industry, paraffins larger than C5 are used for catalytic reform. The catalytic reform is one of the most important processes for petroleum refine in reason of all reactions they drive to production of high-octane products. Reformate has high-octane products, but they contain 60% aromatics. Isomerization of C5- C7 can improve the octane number. The octane number of n-heptane is zero and increases after isomerization. For tri branched C7, the octane number reaches 113, which is higher than that of benzene. So, isomerization of C5-C7 is suggested to be a reasonable way to replace or partly replace the catalytic reforming process. It can decrease aromatics content with enhancement of octane number. Liquid acid catalysts were widely used in chemical industry in past decades. However, they face strong environmental challenges. The heavy corrosion of the reactor system is one of the main problems. Thus, solid acid catalysts are investigated for the isomerization reactions. The aim of this work is to develop a catalysts for the production of reformate products. Isomerization is catalyzed by metal-acid bifunctional catalysts. The metal components aid in hydrogenation, while the support, such as, zirconium, clays or zeolites, is the acidic component. (author)

Bi-metallic catalysts, methods of making, and uses thereof

KAUST Repository

Basset, Jean-Marie

2017-01-19

Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

Bi-metallic catalysts, methods of making, and uses thereof

KAUST Repository

Basset, Jean-Marie; Samantaray, Manoja K.; Dey, Raju; Abou-Hamad, Edy; Kavitake, Santosh

2017-01-01

Provided herein are bi-metallic catalysts, methods of making, and uses thereof. In some embodiments, the bi-metallic catalyst contains two different metal catalysts that can be used in hydrocarbon metathesis reactions, in some embodiments, the methods of making the bi-metallic catalysts can include two steps utilizing a surface organometallic chemistry approach in which the two different metal catalysts are sequentially grafted onto a support.

Two Catalysts for Selective Oxidation of Contaminant Gases

Science.gov (United States)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to

Synergetic mechanism of methanol–steam reforming reaction in a catalytic reactor with electric discharges

International Nuclear Information System (INIS)

Kim, Taegyu; Jo, Sungkwon; Song, Young-Hoon; Lee, Dae Hoon

2014-01-01

Highlights: • Methanol–steam reforming was performed on Cu catalysts under an electric discharge. • Discharge had a synergetic effect on the catalytic reaction for methanol conversion. • Discharge lowered the temperature for catalyst activation or light off. • Discharge controlled the yield and selectivity of species in a reforming process. • Adsorption triggered by a discharge was a possible mechanism for a synergetic effect. - Abstract: Methanol–steam reforming was performed on Cu/ZnO/Al 2 O 3 catalysts under an electric discharge. The discharge occurred between the electrodes where the catalysts were packed. The electric discharge was characterized by the discharge voltage and electric power to generate the discharge. The existence of a discharge had a synergetic effect on the catalytic reaction for methanol conversion. The electric discharge provided modified reaction paths resulting in a lower temperature for catalyst activation or light off. The discharge partially controlled the yield and selectivity of species in a reforming process. The aspect of control was examined in view of the reaction kinetics. The possible mechanisms for the synergetic effect between the catalytic reaction and electric discharge on methanol–steam reforming were addressed. A discrete reaction path, particularly adsorption triggered by an electric discharge, was suggested to be the most likely mechanism for the synergetic effect. These results are expected to provide a guide for understanding the plasma–catalyst hybrid reaction

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

Directory of Open Access Journals (Sweden)

Shouyun Cheng

2016-12-01

Full Text Available The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction, and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.

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.

Hydrogen production via autothermal reforming of Diesel fuel

Energy Technology Data Exchange (ETDEWEB)

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

2004-08-01

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

Hydrogen yield from low temperature steam reforming of ethanol

Energy Technology Data Exchange (ETDEWEB)

Das, N.K.; Dalai, A.K. [Saskatchewan Univ., Saskatoon, SK (Canada). Dept. of Chemical Engineering, Catalysis and Chemical Reaction Engineering Laboratories; Ranganathan, R. [Saskatchewan Research Council, Saskatoon, SK (Canada)

2007-02-15

Interest in the use of ethanol for fuel cell hydrogen production was discussed with particular reference to a study in which the production of hydrogen was maximized through low temperature steam reforming of ethanol in the temperature range of 200 to 360 degrees C. The primary objective of this study was to determine the effect of Mn concentration on a Cu/Al{sub 2}O{sub 3} catalyst for steam reforming of ethanol to produce hydrogen. The purpose was to maximize ethanol conversion and hydrogen selectivity in the lowest possible reaction temperature for the ideal catalyst activity. The optimum reaction conditions in the presence of a suitable catalyst can produce the desired products of hydrogen and carbon dioxide. Cu/Al{sub 2}O{sub 3} catalysts with six different concentrations ranging from 0 to 10 weight per cent Mn, were prepared, characterized and studied for the ethanol-steam reforming reaction. The effects of different process variables were studied, including water-to-ethanol feed ratio, space time and catalyst reduction temperatures on ethanol conversion and hydrogen yield. Maximum ethanol conversion of 60.7 per cent and hydrogen yield of 3.74 (mol of hydrogen per mol of ethanol converted) were observed at 360 degrees C for a catalyst with 2.5 weight per cent Mn loading. 29 refs., 3 tabs., 12 figs.

Fundamentals of Hydrocarbon Upgrading to Liquid Fuels and Commodity Chemicals over Catalytic Metallic Nanoparticles

Science.gov (United States)

Chen, Tao

Promising new technologies for biomass conversion into fuels and chemical feedstocks rely on the production of bio-oils, which need to be upgraded in order to remove oxygen-containing hydrocarbons and water. A high oxygen concentration makes bio-oils acidic and corrosive, unstable during storage, and less energetically valuable per unit weight than petroleum-derived hydrocarbons. Although there are efficient processes for the production of bio-oils, there are no efficient technologies for their upgrading. Current technologies utilize traditional petroleum refining catalysts, which are not optimized for biomass processing. New upgrading technologies are, therefore, urgently needed for development of sustainable energy resources. Development of such new technologies, however, is severely hindered by a lack of fundamental understanding of how oxygen and oxygen-containing hydrocarbons derived from biomass interact with promising noble-metal catalysts. In this study, kinetic reaction measurements, catalyst characterization and quantum chemical calculations using density functional theory were combined for determining adsorption modes and reaction mechanisms of hydrocarbons in the presence of oxygen on surfaces of catalytic noble-metal nanoparticles. The results were used for developing improved catalyst formulations and optimization of reaction conditions. The addition of molybdenum to platinum catalysts was shown to improve catalytic activity, stability, and selectivity in hydrodeoxygenation of acetic acid, which served as a model biomass compound. The fundamental results that describe interactions of oxygen and hydrocarbons with noble-metal catalysts were extended to other reactions and fields of study: evaluation of the reaction mechanism for hydrogen peroxide decomposition, development of improved hydrogenation catalysts and determination of adsorption modes of a spectroscopic probe molecule.

Designing Pd-based supported bimetallic catalysts for environmental applications

OpenAIRE

Nowicka, Ewa; Meenakshisundaram, Sankar

2018-01-01

Supported bimetallic nanoparticulate catalysts are an important class of heterogeneous catalysts for many reactions including selective oxidation, hydrogenation/hydrogenolysis, reforming, biomass conversion reactions, and many more. The activity, selectivity, and stability of these catalysts depend on their structural features including particle size, composition, and morphology. In this review, we present important structural features relevant to supported bimetallic catalysts focusing on Pd...

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.

Synthetic production of fuels by the Fischer Tropsch reaction using iron catalysts

International Nuclear Information System (INIS)

Rodriguez Cepeda, Rodrigo; Pacheco Ochoa, Luis

2004-01-01

A series of iron catalysts were prepared on three different types of supports: alumina and two activated carbons from eucalyptus woods and tagua seeds. Potassium was used as promoter and palladium was deposited by the excess wetness impregnation method. The catalysts were characterized by N 2 adsorption at 77 K, XRD and TPR analysis and evaluated as Fischer-Tropsch catalysts. The carbon supported catalysts favour the production of liquid hydrocarbons and decrease the aqueous phase. Those supported with alumina form gases and aqueous phase as the main products. The α p parameters of the Schulz-Flory distribution show hydrocarbons between gasoline and diesel

Steam Reformer With Fibrous Catalytic Combustor

Science.gov (United States)

Voecks, Gerald E.

1987-01-01

Proposed steam-reforming reactor derives heat from internal combustion on fibrous catalyst. Supplies of fuel and air to combustor controlled to meet demand for heat for steam-reforming reaction. Enables use of less expensive reactor-tube material by limiting temperature to value safe for material yet not so low as to reduce reactor efficiency.

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.

Steam Reforming of CH4 Using Ni- Substituted Pyrochlore Catalysts

Science.gov (United States)

Haynes, Daniel J.

The steam reforming of methane (SMR) continues to remain an important industrial reaction for large-scale production of H2 as well as synthesis gas mixtures which can be used for the production of useful chemicals (e.g. methanol). Although SMR is a rather mature technology, traditional nickel based catalysts used industrially are subjected to severe temperatures and reaction conditions, which lead to irreversible activity loss through sintering, support collapse, and carbon formation. Pyrochlore-based mixed oxide have been identified as refractory materials that can be modified through the substitution of catalytic metals and other promoting species into the structure to mitigate these issues causing deactivation. For this study, a lanthanum zirconate pyrochlore catalyst was substituted with Ni to determine whether the oxide structure could effectively stabilize the activity of the catalytic metal during the SMR. The effect of different variables including calcination temperature, a comparison of a substituted versus supported Ni pyrochlore catalyst, Ni weight loading, and Sr promotion have been evaluated to determine the location of the Ni in the structure, and their effect on catalytic behavior. It was revealed that the effect of calcination temperature on a 6wt% Ni substituted pyrochlore produced by the Pechini method demonstrated very little Ni was soluble in the pyrochlore lattice. It was further revealed that by XRD, TEM, and atom probe tomography that, despite the metal loading, Ni exsolves from the structure upon crystallization of the pyrochlore at 700°C, and forms NiO at the surface and grain boundaries. An additional separate La2ZrNiO6 perovskite phase also began to form at higher temperatures (>800°C). Increasing calcination temperature was found to lead to slight sintering of the NiO at the surface, which made the NiO more reducible. Meanwhile decreasing the Ni weight loading was found to produce a lower reduction temperature due to the presence of

Solar Reforming of Carbon Dioxide to Produce Diesel Fuel

Energy Technology Data Exchange (ETDEWEB)

Dennis Schuetzle; Robert Schuetzle

2010-12-31

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

NOVEL SUPPORTED BIMETALLIC CARBIDE CATALYSTS FOR COPROCESSING OF COAL WITH WASTE METERIALS

Energy Technology Data Exchange (ETDEWEB)

S. Ted Oyama; David F. Cox; Chunshan Song; Fred Allen; Weilin Wang; Viviane Schwartz; Xinqin Wang; Jianli Yang

2001-01-01

The overall objectives of this project are to explore the potential of novel monometallic and bimetallic Mo-based carbide catalysts for heavy hydrocarbon coprocessing, and to understand the fundamental chemistry related to the reaction pathways of coprocessing and the role of the catalysts in the conversion of heavy hydrocarbon resources into liquid fuels based on the model compound reactions.

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

Science.gov (United States)

Narula, Chaitanya K.; Davison, Brian H.

2015-11-13

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

Science.gov (United States)

Narula, Chaitanya K.; Davison, Brian H.

2018-04-17

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

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.

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.

Bifunctional catalysts for the direct production of liquid fuels from syngas

NARCIS (Netherlands)

Sartipi, S.

2014-01-01

Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve

Modification of the performance of WO3-ZrO2 catalysts by metal addition in hydrocarbon reactions

Directory of Open Access Journals (Sweden)

Gerardo Carlos Torres

2012-01-01

Full Text Available A study of the different hydrocarbon reactions over Ni doped WO3-ZrO2 catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition.

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

Science.gov (United States)

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

2015-12-14

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

Low-Temperature Catalytic Performance of Ni-Cu/Al2O3 Catalysts for Gasoline Reforming to Produce Hydrogen Applied in Spark Ignition Engines

Directory of Open Access Journals (Sweden)

Le Anh Tuan

2016-03-01

Full Text Available The performance of Ni-Cu/Al2O3 catalysts for steam reforming (SR of gasoline to produce a hydrogen-rich gas mixture applied in a spark ignition (SI engine was investigated at relatively low temperature. The structural and morphological features and catalysis activity were observed by X-ray diffractometry (XRD, scanning electron microscopy (SEM, and temperature programmed reduction (TPR. The results showed that the addition of copper improved the dispersion of nickel and therefore facilitated the reduction of Ni at low temperature. The highest hydrogen selectivity of 70.6% is observed over the Ni-Cu/Al2O3 catalysts at a steam/carbon ratio of 0.9. With Cu promotion, a gasoline conversion of 42.6% can be achieved at 550 °C, while with both Mo and Ce promotion, the gasoline conversions were 31.7% and 28.3%, respectively, higher than with the conventional Ni catalyst. On the other hand, initial durability testing showed that the conversion of gasoline over Ni-Cu/Al2O3 catalysts slightly decreased after 30 h reaction time.

Investigations on a new internally-heated tubular packed-bed methanol–steam reformer

KAUST Repository

Nehe, Prashant

2015-05-01

Small-scale reformers for hydrogen production through steam reforming of methanol can provide an alternative solution to the demand of continuous supply of hydrogen gas for the operation of Proton Exchange Membrane Fuel Cells (PEMFCs). A packed-bed type reformer is one of the potential designs for such purpose. An externally heated reformer has issues of adverse lower temperature in the core of the reformer and significant heat loss to the environment thus impacting its performance. Experimental and numerical studies on a new concept of internally heated tubular packed-bed methanol-steam reformer have been reported in this paper with improved performance in terms of higher methanol conversion and reduced heat losses to surroundings. CuO/ZnO/Al2O3 is used as the catalyst for the methanol-steam reforming reaction and a rod-type electric heater at the center of the reactor is used for supplying necessary heat for endothermic steam reforming reaction. The vaporizer and the reformer unit with a constant volume catalyst bed are integrated in the annular section of a tubular reformer unit. The performance of the reformer was investigated at various operating conditions like feed rate of water-methanol mixture, mass of the catalyst and reforming temperature. The experimental and numerical results show that the methanol conversion and CO concentration increase with internal heating for a wide range of operating conditions. The developed reformer unit generates 50-80W (based on lower heating value) of hydrogen gas for applications in PEMFCs. For optimized design and operating conditions, the reformer unit produced 298sccm reformed gas containing 70% H2, 27% CO2 and 3% CO at 200-240°C which can produce a power output of 25-32W assuming 60% fuel cell efficiency and 80% of hydrogen utilization in a PEMFC. © 2015 Hydrogen Energy Publications, LLC.

Activity and selectivity of three molybdenum catalysts for coal liquefaction reactions

Energy Technology Data Exchange (ETDEWEB)

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

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

Progress in catalytic naphtha reforming process: A review

International Nuclear Information System (INIS)

Rahimpour, Mohammad Reza; Jafari, Mitra; Iranshahi, Davood

2013-01-01

Catalytic naphtha reforming process is a vital process for refineries due to the production of high-octane components, which is intensely demanded in our modern life. The significance of this industrial process induced researchers to investigate different aspects of catalytic naphtha reforming process intensively. Some of the investigators try to improve this process by representing more effective catalysts, while others try to elucidate its kinetic and deactivation mechanisms and design more efficient reactor setups. The amount of these established papers is so much that may confuse some of the researchers who want to find collective information about catalytic naphtha reforming process. In the present paper, the published studies from 1949 until now are categorized into three main groups including finding suitable catalyst, revealing appropriate kinetic and deactivation model, and suggesting efficient reactor configuration and mode of operation. These studies are reviewed separately, and a suitable reference is provided for those who want to have access to generalized information about catalytic naphtha reforming process. Finally, various suggestions for revamping the catalytic naphtha reforming process have been proposed as a guideline for further investigations

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

Science.gov (United States)

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

2017-09-01

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

Metal-Exchanged β Zeolites as Catalysts for the Conversion of Acetone to Hydrocarbons

Directory of Open Access Journals (Sweden)

Aurora J. Cruz-Cabeza

2012-01-01

Full Text Available Various metal-β zeolites have been synthesized under similar ion-exchange conditions. During the exchange process, the nature and acid strength of the used cations modified the composition and textural properties as well as the Brönsted and Lewis acidity of the final materials. Zeolites exchanged with divalent cations showed a clear decrease of their surface Brönsted acidity and an increase of their Lewis acidity. All materials were active as catalysts for the transformation of acetone into hydrocarbons. Although the protonic zeolite was the most active in the acetone conversion (96.8% conversion, the metal-exchanged zeolites showed varied selectivities towards different products of the reaction. In particular, we found the Cu-β to have a considerable selectivity towards the production of isobutene from acetone (over 31% yield compared to 7.5% of the protonic zeolite. We propose different reactions mechanisms in order to explain the final product distributions.

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.)

Multi-stage catalyst systems and uses thereof

Science.gov (United States)

Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

2009-02-10

Catalyst systems and methods provide benefits in reducing the content of nitrogen oxides in a gaseous stream containing nitric oxide (NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2). The catalyst system comprises an oxidation catalyst comprising a first metal supported on a first inorganic oxide for catalyzing the oxidation of NO to nitrogen dioxide (NO.sub.2), and a reduction catalyst comprising a second metal supported on a second inorganic oxide for catalyzing the reduction of NO.sub.2 to nitrogen (N.sub.2).

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.

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.

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.

Active carbon catalyst for heavy oil upgrading

Energy Technology Data Exchange (ETDEWEB)

Fukuyama, Hidetsugu; Terai, Satoshi [Technology Research Center, Toyo Engineering Corporation, 1818 Azafujimi, Togo, Mobara-shi, Chiba 297-00017 (Japan); Uchida, Masayuki [Business Planning and Exploring Department, Overseas Business Development and Marketing Division, Toyo Engineering Corporation, 2-8-1 Akanehama, Narashino-shi, Chiba 275-0024 (Japan); Cano, Jose L.; Ancheyta, Jorge [Maya Crude Treatment Project, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, Col. San Bartolo Atepehuacan, Mexico D.F. 07730 (Mexico)

2004-11-24

The active carbon (AC) catalyst was studied by hydrocracking of Middle Eastern vacuum residue (VR) for heavy oil upgrading. It was observed that the active carbon has the affinity to heavy hydrocarbon compounds and adsorption selectivity to asphaltenes, and exhibits better ability to restrict the coke formation during the hydrocracking reaction of VR. The mesopore of active carbon was thought to play an important role for effective conversion of heavy hydrocarbon compounds into lighter fractions restricting carbon formation. The performance of the AC catalyst was examined by continuous hydrocracking by CSTR for the removal of such impurities as sulfur and heavy metals (nickel and vanadium), which are mostly concentrated in the asphaltenes. The AC catalyst was confirmed to be very effective for the removal of heavy metals from Middle Eastern VR, Maya/Istmo VR and Maya VR. The extruded AC catalysts were produced by industrial manufacturing method. The application test of the extruded AC catalyst for ebullating-bed reactor as one of the commercially applicable reactors was carried out at the ebullating-bed pilot plant for 500h. The ebullition of the extruded AC catalyst was successfully traced and confirmed by existing {gamma}-ray density meter. The extruded AC catalyst showed stable performance with less sediment formation at an equivalent conversion by conventional alumina catalyst at commercial ebullating-bed unit. The degradation of the AC catalyst at the aging test was observed to be less than that of the conventional alumina catalyst. Thus, the AC catalyst was confirmed to be effective and suitable for upgrading of heavy oil, especially such heavy oils as Maya, which contains much heavy metals.

Process for conversion of lignin to reformulated hydrocarbon gasoline

Science.gov (United States)

Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

1999-09-28

A process for converting lignin into high-quality reformulated hydrocarbon gasoline compositions in high yields is disclosed. The process is a two-stage, catalytic reaction process that produces a reformulated hydrocarbon gasoline product with a controlled amount of aromatics. In the first stage, a lignin material is subjected to a base-catalyzed depolymerization reaction in the presence of a supercritical alcohol as a reaction medium, to thereby produce a depolymerized lignin product. In the second stage, the depolymerized lignin product is subjected to a sequential two-step hydroprocessing reaction to produce a reformulated hydrocarbon gasoline product. In the first hydroprocessing step, the depolymerized lignin is contacted with a hydrodeoxygenation catalyst to produce a hydrodeoxygenated intermediate product. In the second hydroprocessing step, the hydrodeoxygenated intermediate product is contacted with a hydrocracking/ring hydrogenation catalyst to produce the reformulated hydrocarbon gasoline product which includes various desirable naphthenic and paraffinic compounds.

Analysis of coke precursor on catalyst and study on regeneration of catalyst in upgrading of bio-oil

International Nuclear Information System (INIS)

Guo, Xiaoya; Zheng, Yong; Zhang, Baohua; Chen, Jinyang

2009-01-01

Catalyst HZSM-5 was used in bio-oil catalytic cracking upgrading. The precursor of coke on the catalyst was analyzed by means of TGA, FTIR and C13 NMR. Precursors of coke deposited in the pore of the molecular sieve were mainly aromatic hydrocarbon with the boiling point range from 350 o C to 650 o C. Those on the outer surface of the pellet precursor were identified as saturated aliphatic hydrocarbons with the boiling point below 200 o C. The activity of HZSM-5 was studied after regeneration. In terms of yield of organic distillate and formation rate of coke, results showed that catalytic activity change moderately during the first three times of regeneration.

Methanol steam-reforming in a catalytic fixed bed reactor

Energy Technology Data Exchange (ETDEWEB)

Duesterwald, H G; Hoehlein, B; Kraut, H; Meusinger, J; Peters, R [Research Centre Juelich (KFA) (Germany). Inst. of Energy Process Engineering; Stimming, U [Technische Univ. Muenchen, Garching (Germany). Inst. fuer Festkoerperphysik und Techn. Phys.

1997-12-01

Designing an appropriate methanol steam reformer requires detailed knowledge about the processes within such a reactor. Thus, the axial temperature and concentration gradients and catalyst ageing were investigated. It was found that for a fresh catalyst load, the catalyst located in the reactor entrance was most active during the experiment. The activity of this part of the catalyst bed decreased after some time of operation due to ageing. With further operation, the most active zone moved through the catalyst bed. From the results concerning hydrogen production and catalyst degradation, the necessary amount of catalyst for a mobile PEMFC-system can be estimated. (orig.)

Recovery of hydrocarbon oils

Energy Technology Data Exchange (ETDEWEB)

1941-02-10

A process is disclosed for recovery of hydrocarbon oils, especially lubricating oils or diesel oils, through pressure hydrogenation of distillation, extraction of hydrogenation products from coal or coaly materials or from oils such as mineral oils or tars in liquid phase by use in a reaction vessel of fixed-bed catalysts, characterized in that as starting material is employed material which has been freed of asphaltic and resinous material by hydrogenation refining, vacuum-steam distillation, treatment with hydrogen-rich hydrocarbons (hydroforming), or sulfuric acid.

Kinetics of catalytic reforming with Pt-Sn catalyst; Modelisation cinetique du reformage catalytique sur catalyseur Pt-Sn/Al{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Cochegrue, H.

2001-04-01

Catalytic Reforming is one of the key processes for petrol refining as it produces gasoline with a high octane number and it is a main source of hydrogen. Refiners are asking for more accurate models in order to optimise their plants. An innovative methodology called 'Single Events' is very different from the classical empirical models because it takes into account the various reaction intermediates and reaction pathways. Some hypotheses based on the relative stability of the carbo-cations allow to get a small number of parameters, which are independent of the composition of the feedstock used. The main target of this work was to apply this methodology to the Catalytic Reforming. The single event network had to be first reduced to a late lumped reaction scheme, which incorporates the detailed knowledge of the elementary network while the intermediates and the reaction pathways are reduced: it can be applied now to naphtha feedstock, although the detailed composition is not yet well known. A pilot unit of Catalytic Reforming, which is representative of the industrial processes, was first designed for the kinetic experiments. Experiments with technical heptane were conducted with a fresh catalyst, which was cocked first, and with a used catalyst from a refinery plant. This latter was difficult to use because of its fast deactivation. However, the results obtained allowed to study the influence of the experimental parameters and of the poisoning by iron, and to estimate some of the main kinetic parameters of the model. (author)

Session 4: The influence of elementary heterogeneous reforming chemistry within solid-oxide fuel cell anodes

Energy Technology Data Exchange (ETDEWEB)

Zhu, H.; Kee, R.J. [Engineering Division, Colorado School of Mines, Golden, CO (United States); Janardhanan, V.M.; Deutschmann, O. [Karlsruhe Univ., Institute for Chemical Technology (Germany); Goodwin, D.G. [Engineering and Applied Science., California Inst. of Technology, Pasadena, CA (United States); Sullivan, N.P. [ITN Energy Systems, Littleton, CO (United States)

2004-07-01

In the work presented a computational model is developed that represents the coupled effects of fluid flow in fuel channels, porous media transport and chemistry in the anode, and electrochemistry associated with the membrane-electrode assembly. An important objective is to explore the role of heterogeneous chemistry within the anode. In addition to cell electrical performance the chemistry model predicts important behaviors like catalyst-fouling deposit formation (i.e., coking). The model is applied to investigate alternative fuel-cell operating conditions, including varying fuel flow rates, adding air to the fuel stream, and recirculating exhaust gases. Results include assessments of performance metrics like fuel utilization, cell efficiency, power density, and catalyst coking. The model shows that 'direct electrochemical oxidation' of hydrocarbon fuels in solid-oxide fuel cells can be explained by a process that involves reforming the fuel to H{sub 2}, with hydrogen being the only species responsible for charge exchange. The model can be applied to investigate alternative design and operating conditions, seeking to improve the overall performance. (O.M.)

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.)

Modeling of an axial flow, spherical packed-bed reactor for naphtha reforming process in the presence of the catalyst deactivation

Energy Technology Data Exchange (ETDEWEB)

Iranshahi, D.; Pourazadi, E.; Paymooni, K.; Bahmanpour, A.M.; Rahimpour, M.R.; Shariati, A. [Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of)

2010-12-15

Improving the octane number of the aromatics' compounds has always been an important matter in refineries and lots of investigations have been made concerning this issue. In this study, an axial-flow spherical packed-bed reactor (AF-SPBR) is considered for naphtha reforming process in the presence of catalyst deactivation. Model equations are solved by the orthogonal collocation method. The AF-SPBR results are compared with the plant data of a conventional tubular packed-bed reactor (TR). The effects of some important parameters such as pressure and temperature on aromatic and hydrogen production rates and catalyst activity have been investigated. Higher production rates of aromatics can successfully be achieved in this novel reactor. Moreover, results show the capability of flow augmentation in the proposed configuration in comparison with the TR. This study shows the superiority of AF-SPBR configuration to the conventional types. (author)

Development of a basic numerical model of an isooctane catalytic autothermal reformer for an automobile

International Nuclear Information System (INIS)

Li, V.C.L.; Harrison, S.; Oosthuizen, P.; Peppley, B.

2004-01-01

'Full text:' A numerical study of the performance of an isooctane catalytic autothermal reformer for a fuel cell automobile has been undertaken. The prototype reformer considered in this study, which is a tubular reformer with three annular sections, was designed and built at the Royal Military College of Canada (RMC). The flow within the reformer was assumed to be steady. The different chemical reactions, along with the reaction rate constants, that take place over the autothermal reforming catalyst (a ceria-based platinum catalyst), were obtained through the analysis and regression of the experimental results from the literature. By neglecting the radial gradients in the concentrations and the velocities of the various species in the flow and in the temperature of the reformer, a one-dimensional numerical model, based on the molar flow rate differential equations and energy equation, was developed to simulate the composition and temperature profiles along the length of the catalyst bed. The results obtained from the numerical model were verified against published results. Numerical results were obtained for a range of total inlet flow rates, different inlet temperatures of the fuel mixture and different oxygen concentrations in feed air at the inlet of the reformer. (author)

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.

Simulation study of a proton exchange membrane (PEM) fuel cell system with autothermal reforming

Energy Technology Data Exchange (ETDEWEB)

Ersoz, Atilla [TUBITAK Marmara Research Centre, Energy Systems and Environmental Research Institute, 41470 Gebze, Kocaeli (Turkey); Olgun, Hayati [TUBITAK Marmara Research Centre, Energy Systems and Environmental Research Institute, 41470 Gebze, Kocaeli (Turkey); Ozdogan, Sibel [Marmara University, Faculty of Engineering, Department of Mechanical Engineering, 81040 Goztepe, Istanbul (Turkey)

2006-08-15

This paper presents the results of a study for a 100 kW net electrical power PEM fuel cell system. The major system components are an autothermal reformer, high and low temperature shift reactors, a preferential oxidation reactor, a PEM fuel cell, a combustor and an expander. Intensive heat integration within the PEM fuel cell system has been necessary to achieve acceptable net electrical efficiency levels. The calculations comprise the auxiliary equipment such as pumps, compressors, heaters, coolers, heat exchangers and pipes. The process simulation package 'ASPEN-HYSYS 3.1' has been used along with conventional calculations. The operation conditions of the autothermal reformer have been studied in detail to determine the values, which lead to the production of a hydrogen rich gas mixture with CO concentration at ppm level. The operation parameters of the other reactors have been determined considering the limitations implied by the catalysts involved. A gasoline type hydrocarbon fuel has been studied as the source for hydrogen production. The chemical composition of the hydrocarbon fuel affects the favorable operation conditions of autothermal reforming and the following fuel purification steps. Thermal efficiencies have been calculated for all of the major system components for selected operation conditions. The fuel cell stack efficiency has been calculated as a function of the number of cells (500-1250 cells). Efficiencies of all of the major system components along with auxiliary unit efficiencies determine the net electrical efficiency of the PEM fuel cell system. The obtained net electrical efficiency levels are between 30 (500 cells) and 37% (1250 cells). Hence, they are comparable with or higher than those of the conventional gasoline based internal combustion engine systems, in terms of the mechanical power efficiency.

Simulation study of a proton exchange membrane (PEM) fuel cell system with autothermal reforming

International Nuclear Information System (INIS)

Ersoz, Atilla; Olgun, Hayati; Ozdogan, Sibel

2006-01-01

This paper presents the results of a study for a 100 kW net electrical power PEM fuel cell system. The major system components are an autothermal reformer, high and low temperature shift reactors, a preferential oxidation reactor, a PEM fuel cell, a combustor and an expander. Intensive heat integration within the PEM fuel cell system has been necessary to achieve acceptable net electrical efficiency levels. The calculations comprise the auxiliary equipment such as pumps, compressors, heaters, coolers, heat exchangers and pipes. The process simulation package 'ASPEN-HYSYS 3.1' has been used along with conventional calculations. The operation conditions of the autothermal reformer have been studied in detail to determine the values, which lead to the production of a hydrogen rich gas mixture with CO concentration at ppm level. The operation parameters of the other reactors have been determined considering the limitations implied by the catalysts involved. A gasoline type hydrocarbon fuel has been studied as the source for hydrogen production. The chemical composition of the hydrocarbon fuel affects the favorable operation conditions of autothermal reforming and the following fuel purification steps. Thermal efficiencies have been calculated for all of the major system components for selected operation conditions. The fuel cell stack efficiency has been calculated as a function of the number of cells (500-1250 cells). Efficiencies of all of the major system components along with auxiliary unit efficiencies determine the net electrical efficiency of the PEM fuel cell system. The obtained net electrical efficiency levels are between 30 (500 cells) and 37% (1250 cells). Hence, they are comparable with or higher than those of the conventional gasoline based internal combustion engine systems, in terms of the mechanical power efficiency

Reforming technology for syngas production

International Nuclear Information System (INIS)

Epstein, M.

1997-01-01

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

Micelle-derived catalysts for extended Schulz-Flory. Technical progress report, July 1, 1986--September 30, 1986

Energy Technology Data Exchange (ETDEWEB)

Abrevaya, H.

1986-12-31

The objective of this program is to develop a synthesis gas conversion catalyst with higher selectivity to liquid fuels, while maintaining catalytic activity and stability at least equivalent relative to state-of-the-art precipitated iron catalysts. During this quarter, the emphasis in the program has been the investigation of the hydrocarbon cutoff hypothesis with supported ruthenium catalysts. An alumina-supported catalyst with smaller than 20{Angstrom} ruthenium particles was tested under conditions of maximal water gas shift activity. During this test more than 90% of the water made in the Fischer-Tropsch synthesis reaction was converted to H{sub 2}. However, the extent of ruthenium metal agglomeration was not reduced. Accordingly, it was not possible to conclude whether hydrocarbon cutoff occurs with smaller than 20{Angstrom} ruthenium particles on {gamma}-alumina. A ruthenium catalyst prepared on Y-type zeolite had 20{Angstrom} or smaller ruthenium particles according to STEM examination and a 15{Angstrom} average ruthenium metal particle size according to EXAFS examination. The ruthenium metal particle size was stable during the test with this catalyst. The hydrocarbon product distribution was Anderson-Schulz-Flory with no cutoff up to a carbon number of 160. A well-dispersed titania-supported ruthenium catalyst is going to be evaluated during the next quarter in order to determine whether hydrocarbon cutoff occurs.

Dynamic modeling of a three-stage low-temperature ethanol reformer for fuel cell application

Energy Technology Data Exchange (ETDEWEB)

Garcia, Vanesa M; Serra, Maria [Institut de Robotica i Informatica Industrial (CSIC-UPC), Llorens i Artigas 4-6, 08028 Barcelona (Spain); Lopez, Eduardo; Llorca, Jordi [Institut de Tecniques Energetiques, Universitat Politecnica de Catalunya, Diagonal 647, ed. ETSEIB, 08028 Barcelona (Spain)

2009-07-01

A low-temperature ethanol reformer based on a cobalt catalyst for the production of hydrogen has been designed aiming the feed of a fuel cell for an autonomous low-scale power production unit. The reformer comprises three stages: ethanol dehydrogenation to acetaldehyde and hydrogen over SnO{sub 2} followed by acetaldehyde steam reforming over Co(Fe)/ZnO catalyst and water gas shift reaction. Kinetic data have been obtained under different experimental conditions and a dynamic model has been developed for a tubular reformer loaded with catalytic monoliths for the production of the hydrogen required to feed a 1 kW PEMFC. (author)

Catalysts for conversion of syngas to liquid motor fuels

Science.gov (United States)

Rabo, Jule A.; Coughlin, Peter K.

1987-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst composition capable of ensuring the production of only relatively minor amounts of heavy products boiling beyond the diesel oil range. The catalyst composition, having desirable stability during continuous production operation, employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component. The latter component is a steam-stabilized zeolite Y catalyst of hydrophobic character, desirably in acid-extracted form.

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

International Nuclear Information System (INIS)

Ni Meng

2013-01-01

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

Upgrading pyrolysis bio-oil to biofuel over bifunctional Co-Zn/HZSM-5 catalyst in supercritical methanol

International Nuclear Information System (INIS)

Cheng, Shouyun; Wei, Lin; Julson, James; Muthukumarappan, Kasiviswanathan; Kharel, Parashu Ram

2017-01-01

Highlights: • Integration of Co-Zn/HZSM-5 and supercritical methanol was used for bio-oil hydrodeoxygenation. • Co-Zn/HZSM-5 exhibited higher effectiveness than Co/HZSM-5 or Zn/HZSM-5. • 15%Co5%Zn/HZSM-5 produced biofuel with the highest hydrocarbons content at 35.33%. • Loading of Co and/or Zn did not change crystalline structure of HZSM-5. • Hydrogenation and esterification are main reactions in bio-oil hydrodeoxygenation. - Abstract: The role of catalyst is essential in processes of upgrading biomass pyrolysis bio-oil into hydrocarbon biofuel. While the majority of heterogeneous catalytic processes are conducted in the presence of gas (nearly ideal) or liquid phase, a growing number of processes are utilizing supercritical fluids (SCFs) as reaction media. Although hydrodeoxygenation (HDO) is proven a promising process for pyrolysis bio-oil upgrading to hydrocarbon biofuel, catalyst efficiency remains a challenge. Integrating heterogeneous catalysts with SCFs in a bio-oil HDO process was investigated in this study. Bifunctional Co-Zn/HZSM-5 catalysts were firstly used to upgrade bio-oil to biofuel in supercritical methanol. The loading of Co and Zn did not change HZSM-5 crystalline structure. Physicochemical properties of biofuel produced by Co and/or Zn loaded HZSM-5 catalysts such as water content, total acid number, viscosity and higher heating value improved. Bimetallic Co-Zn/HZSM-5 catalysts showed enhanced reactions of decarboxylation and decarbonylation that resulted in higher yields of CO and CO 2 . Bimetallic Co-Zn/HZSM-5 catalysts were more effective for bio-oil HDO than monometallic Co/HZSM-5 or Zn/HZSM-5 catalyst , which was attributed to the synergistic effect of Co and Zn on HZSM-5 support. Bimetallic Co-Zn/HZSM-5 catalysts increased biofuel yields and hydrocarbons contents in biofuels in comparison with monometallic Co/HZSM-5 and Zn/HZSM-5 catalysts. 5%Co15%Zn/HZSM-5 catalyst generated the highest biofuel yield at 22.13 wt.%, and 15%Co5

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...

Catalytic reforming of toluene as tar model compound: effect of Ce and Ce-Mg promoter using Ni/olivine catalyst.

Science.gov (United States)

Zhang, Ruiqin; Wang, Huajian; Hou, Xiaoxue

2014-02-01

Tar produced by biomass gasification as a route of renewable energy must be removed before the gas can be used. This study was undertaken using toluene as a model tar compound for evaluating its steam reforming conversion with three Ni-based catalysts, Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. Effects of Ce and Mg promoters on the reaction activity and coke deposition were studied. Overall the performance of Ce and Mg promoted Ni/olivine catalysts is better than that of only Ce promoter and Ni/olivine alone. The experimental results indicate that Ni-Ce-Mg/olivine catalysts could improve the resistance to carbon deposition, enhance energy gases yield and resist 10ppm H2S poison at 100mLmin(-1) for up to 400min. Furthermore, the activity of catalysts was related to the steam/carbon (S/C) ratios; at S/C ratio=5, T=790°C, space velocity=782h(-1) and t=2h, the Ni-Ce-Mg/olivine system yielded 89% toluene conversion, 5.6Lh(-1) product gas rate, 62.6mol% H2 content and 10% (mol useful gas mol(-1) toluene) energy yield. Moreover, at low S/C ratio, it had higher reaction activity and better ability to prevent coking. There is a small amount of carbon deposition in the form of amorphous carbon after 7h. Various characterization techniques such as XRD, FTIR and thermogravimetric were performed to investigate the coke deposition of Ni/olivine, Ni-Ce/olivine and Ni-Ce-Mg/olivine. It is suggested that 3% Ni-1% Ce-1% Mg/olivine was the most promising catalyst due to its minimum coke amount and the lower activation energy of coke burning. Copyright © 2014. Published by Elsevier Ltd.

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.

Oxygen-containing coke species in zeolite-catalyzed conversion of methanol to hydrocarbons

KAUST Repository

Liu, Zhaohui; Dong, Xinglong; Liu, Xin; Han, Yu

2016-01-01

Zeolites are the most commonly used catalysts for methanol-to-hydrocarbon (MTH) conversion. Here, we identified two oxygen-containing compounds as coke species in zeolite catalysts after MTH reactions. We investigated the possible influences

Catalytic Reforming of Oxygenates: State of the Art and Future Prospects.

Science.gov (United States)

Li, Di; Li, Xinyu; Gong, Jinlong

2016-10-12

This Review describes recent advances in the design, synthesis, reactivity, selectivity, structural, and electronic properties of the catalysts for reforming of a variety of oxygenates (e.g., from simple monoalcohols to higher polyols, then to sugars, phenols, and finally complicated mixtures like bio-oil). A comprehensive exploration of the structure-activity relationship in catalytic reforming of oxygenates is carried out, assisted by state-of-the-art characterization techniques and computational tools. Critical emphasis has been given on the mechanisms of these heterogeneous-catalyzed reactions and especially on the nature of the active catalytic sites and reaction pathways. Similarities and differences (reaction mechanisms, design and synthesis of catalysts, as well as catalytic systems) in the reforming process of these oxygenates will also be discussed. A critical overview is then provided regarding the challenges and opportunities for research in this area with a focus on the roles that systems of heterogeneous catalysis, reaction engineering, and materials science can play in the near future. This Review aims to present insights into the intrinsic mechanism involved in catalytic reforming and provides guidance to the development of novel catalysts and processes for the efficient utilization of oxygenates for energy and environmental purposes.

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

Methanol reformer with water vapor and oxygen in catalysts of Cu/CeO2-ZrO2 to generate H2

International Nuclear Information System (INIS)

Aguila M, M.M.

2007-01-01

The environmental pollution is one of the problems more important to solve in the present time because its affect the quality of the alive beings' life. For such a reason alternatives have been looked for to diminish the percentage of air pollution (NO x , CO x , SO x , etc.), for they have been developed it the well-known catalytic converters. Another possibility is the energy use through fuel cells in vehicles using H 2 as fuel free of CO (smaller concentration to 10 ppm). Processes exist for the production of H 2 starting from the methanol and in this work the one was used reformed of methanol with water vapor and oxygen (OSRM) as the main reaction of this work. The primordial objective of this work consists on studying the catalytic properties of the copper (Cu) supported in mixed oxides (ZrO 2 -CeO 2 ) in the reaction of having reformed of methanol with water vapor and oxygen for the production of H 2 . Zirconia is synthesized (ZrO 2 ) and mixed oxides ZrO 2 -CeO 2 (with different relationship Zr/Ce) for the sol-gel method and the one cerium oxide (CeO 2 ) by direct combustion of the cerium nitrate. The oxides were stabilized thermally at 600 C by 5h. The catalysts were prepared by classic impregnation using copper acetate, the nominal concentration was of 3% in weight. The catalysts were roasted at 350 C and later on reduced in flow from H 2 to 350 C for 1h. The characterization of the catalytic materials is carried out through different techniques as: adsorption-desorption of nitrogen to determine the surface area BET, scanning electron microscopy (SEM) to determine the final morphology of the catalysts, X-ray diffraction (XRD) to identify the crystalline phases of the catalytic materials and reduction to programmed temperature (TPR) to evidence the interaction metal-support. The catalytic properties of the catalysts were studied in the reaction CH 3 OH + H 2 O + O 2 , to determine the activity and selectivity. The surface area of the mixed oxides was

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

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

Catalytic pyrolysis of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Vail' eva, N A; Buyanov, R A

1979-01-01

Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

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

International Nuclear Information System (INIS)

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

2017-01-01

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