Production of Syngas by Direct Catalytic Oxidation of Methane
15 Jan 1993-Science (American Association for the Advancement of Science)-Vol. 259, Iss: 5093, pp 343-346
TL;DR: Rhodium was considerably superior to platinum in producing more H2 and less H2O, which can be explained by the known chemistry and kinetics of reactants, intermediates, and products on these surfaces.
Abstract: The reaction between methane and oxygen over platinum and rhodium surfaces in metalcoated ceramic monoliths can be made to produce mostly hydrogen and carbon monoxide (greater than 90% selectivity for both) with almost complete conversion of methane and oxygen at reaction times as short as 10–3 seconds. This process has great promise for conversion of abundant natural gas into liquid products such as methanol and hydrocarbons, which can be easily transported from remote locations. Rhodium was considerably superior to platinum in producing more H2 and less H2O, which can be explained by the known chemistry and kinetics of reactants, intermediates, and products on these surfaces.
Citations
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National Institute of Advanced Industrial Science and Technology1, University of Bari2, Air Products & Chemicals3, University of Delaware4, University of Pittsburgh5, University of California, Berkeley6, California Institute of Technology7, Brookhaven National Laboratory8, Karlsruhe Institute of Technology9, Environmental Molecular Sciences Laboratory10, Tokyo Institute of Technology11, National Renewable Energy Laboratory12, Los Alamos National Laboratory13, University of Louisville14, Texas A&M University15, Sandia National Laboratories16, Northwestern University17, DuPont18, Emory University19, University of Oklahoma20, University of Southern California21, University of Minnesota22, Pennsylvania State University23, Idaho National Laboratory24
TL;DR: The goal of the "Opportunities for Catalysis Research in Carbon Management" workshop was to review within the context of greenhouse gas/carbon issues the current state of knowledge, barriers to further scientific and technological progress, and basic scientific research needs in the areas of H2 generation and utilization.
Abstract: There is increased recognition by the world’s scientific, industrial, and political communities that the concentrations of greenhouse gases in the earth’s
atmosphere, particularly CO_2, are increasing. For
example, recent studies of Antarctic ice cores to
depths of over 3600 m, spanning over 420 000 years,
indicate an 80 ppm increase in atmospheric CO_2 in
the past 200 years (with most of this increase
occurring in the past 50 years) compared to the
previous 80 ppm increase that required 10 000 years.2
The 160 nation Framework Convention for Climate
Change (FCCC) in Kyoto focused world attention on
possible links between CO2 and future climate change
and active discussion of these issues continues.3 In
the United States, the PCAST report4 “Federal
Energy Research and Development for the Challenges
of the Twenty First Century” focused attention
on the growing worldwide demand for energy and the
need to move away from current fossil fuel utilization.
According to the U.S. DOE Energy Information
Administration,5 carbon emission from the transportation
(air, ground, sea), industrial (heavy manufacturing,
agriculture, construction, mining, chemicals,
petroleum), buildings (internal heating, cooling, lighting),
and electrical (power generation) sectors of the
World economy amounted to ca. 1823 million metric
tons (MMT) in 1990, with an estimated increase to
2466 MMT in 2008-2012 (Table 1).
1,220 citations
TL;DR: Several novel synthetic reactions of arenes and alkanes discovered and investigated in the laboratory are summarized here.
Abstract: Several novel synthetic reactions of arenes and alkanes discovered and investigated in our laboratory are summarized here. These include olefin arylation, hydroarylation of alkynes, hydroxylation of arenes, carboxylation of arenes and alkanes, and aminomethylation and acetoxylation of alkanes. Most of these reactions are catalyzed by highly electrophilic transition metal cationic species generated in situ in an acid medium, involving electrophilic metalation of C−H bonds of arenes and alkanes which lead to the formation of aryl−metal and alkyl−metal σ-complexes.
1,212 citations
1,055 citations
TL;DR: A review of the use of catalysis for the current and future production of H2 can be found in this article, where a number of different, largely catalytic approaches for producing H2 are described.
Abstract: This review describes a number of different, largely catalytic approaches for producing H2. Since a major fraction of the world's H2 is produced by catalytic processes, involving multiple steps with different types of catalysts, it is clear that catalysis plays a critical role in the production of H2. This review is focused on the use of catalysis for the current and future production of H2. Some background will be provided to give a perspective of the dramatic change in the supply and demand for H2 in the past decade, followed by a review of how it is produced commercially, with a view to how multiple types of catalysis contribute to the total process for H2 production. Steam methane reforming, the major approach for H2 manufacture, will be a focal point for most of the discussion in pointing out the large number of catalytic steps that are used in this major technology. Finally, some alternative catalytic approaches for H2 production will be described.
794 citations
TL;DR: In this article, an extensive table on contributions to catalytic partial oxidation of methane over transition metal catalysts in the literature is provided, and both theoretical and experimental evidence pointing to inherent differences in the reaction mechanism over transition metals.
Abstract: Catalytic partial oxidation of methane has been reviewed with an emphasis on the reaction mechanisms over transition metal catalysts. The thermodynamics and aspects related to heat and mass transport is also evaluated, and an extensive table on research contributions to methane partial oxidation over transition metal catalysts in the literature is provided. Presented are both theoretical and experimental evidence pointing to inherent differences in the reaction mechanism over transition metals. These differences are related to methane dissociation, binding site preferences, the stability of OH surface species, surface residence times of active species and contributions from lattice oxygen atoms and support species. Methane dissociation requires a reduced metal surface, but at elevated temperatures oxides of active species may be reduced by direct interaction with methane or from the reaction with H, H2, C or CO. The comparison of elementary reaction steps on Pt and Rh illustrates that a key factor to produce hydrogen as a primary product is a high activation energy barrier to the formation of OH. Another essential property for the formation of H2 and CO as primary products is a low surface coverage of intermediates, such that the probability of O–H, OH–H and CO–O interactions are reduced. The local concentrations of reactants and products change rapidly through the catalyst bed. This influences the reaction mechanisms, but the product composition is typically close to equilibrated at the bed exit temperature.
697 citations
References
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TL;DR: In this paper, the authors characterized the phase composition of the NiO/Al 2 O 3 phase of a 25 wt% NiO+Al 2O 3 catalyst for complete oxidation of methane feed to CO 2 and H 2 O. The authors showed that the previously calcined catalyst bed consists of three different regions.
703 citations
TL;DR: Observation of crystals of pure encapsulated α-LaC2 that were exposed to air for several days before analysis indicates that the LaC2 is protected from degradation by the carbon polyhedral shells of the nanoparticles, a new class of materials that can be protected in their pure or carbide forms and may have interesting and useful properties.
Abstract: Single-domain microcrystals of LaC2 encapsulated within nanoscale polyhedral carbon particles have been synthesized in a carbon arc. Typical particle sizes are on the order of 20 to 40 nanometers. The stoichiometry and phase of the La-containing crystals have been assigned from characteristic lattice spacings observed by high-resolution transmission electron microscopy and energy dispersive spectroscopy (EDS). EDS spectra show that La and C are the only elements present. Characteristic interatomic distances of 3.39 and 2.78 angstroms identify the compound inside the nanoparticle cavities as α-LaC2, the phase of LaC2 that is stable at room temperature. Bulk α-LaC2 is metallic and hydrolytic. Observation of crystals of pure encapsulated α-LaC2 that were exposed to air for several days before analysis indicates that the LaC2 is protected from degradation bythe carbon polyhedral shells of the nanoparticles. A high percentage of the carbon nanoparticles have encapsulated LaC2 single crystals. These carbon-coated metal crystals form a new class of materials that can be protected in their pure or carbide forms and may have interesting and useful properties.
609 citations
TL;DR: In this article, it was shown that the partial oxidation of methane to synthesis gas can be carried out at temperatures of only ∼775 °C by using lanthanide ruthenium oxide catalysts.
Abstract: THE diminishing reserves of petroleum oil have focused attention on the possibility of making more efficient use of natural gas, reserves of which are at present considerably under-utilized. Methane is commonly used as a fuel, but it is also the starting material for the production, by steam reforming, of synthesis gas (carbon monoxide and hydrogen), which acts as a feedstock for the synthesis of ammonia and methanol, and can be converted to higher hydrocarbons, alcohols and aldehydes by Fischer–Tropsch catalysis1. The partial oxidation of methane to synthesis gas is also an established industrial process2 but operates at very high temperatures (> 1,200 °C). Here we report that this reaction can be carried out at temperatures of only ∼775 °C by using lanthanide ruthenium oxide catalysts.
591 citations
TL;DR: In this paper, the authors studied the reaction of carbon monoxide catalyzed by Pt(111) using reactive molecular beam-surface scattering and showed that at low coverage, the reaction proceeds with an activation energy E*LH =24.1 kcal/mole and a pre-exponential υ4 =0.11 cm2 particles−1
Abstract: The oxidation of carbon monoxide catalyzed by Pt(111) was studied in ultrahigh vacuum using reactive molecular beam–surface scattering. Under all conditions studied, the reaction follows a Langmuir–Hinshelwood mechanism: the combination of a chemisorbed CO molecule and an oxygen adatom. When both reactants are at low coverage, the reaction proceeds with an activation energy E*LH =24.1 kcal/mole and a pre‐exponential υ4 =0.11 cm2 particles−1 sec−1. At very high oxygen coverage, E*LH decreases to about 11.7 kcal/mole and υ4 to about 2×10−6 cm2 particles−1 sec−1. This is largely attributed to the corresponding increase in the energy of the adsorbed reactants. When a CO molecule incident from the gas phase strikes the surface presaturated with oxygen, it enters a weakly held precursor state to chemisorption. Desorption from this state causes a decrease in chemisorption probability with temperature. Once chemisorbed, the CO molecule then has almost unit probability of reacting to produce CO2 below 540 K. The CO2 product angular distribution varies from cosγ to cos4γ depending sensitively upon the adsorbed reactant concentrations.
522 citations
TL;DR: In this paper, the kinetics of the CO-O2 and CO-NO reactions over single crystal Rh(111) and over alumina-supported Rh catalysts have been compared at realistic reactant pressures.
444 citations