Partial oxidation of methane over silica supported molybdenum oxide catalysts

Two kinds of MoO₃/SiO₂ catalysts, MoO₃-I and MoO₃-S, were prepared by impregnation and sol-gel method, respectively. When MoO₃ loading was increased, formation of MoO₃ crystals was observed to begin at a MoO₃ loading of 8 and 16 wt% with MoO₃-I and MoO₃-S, respectively. The highest yield of formaldehyde from methane oxidation was attained also at those critical values of MoO₃ loading of 8 and 16 wt% over MoO₃-I and MoO₃-S, respectively. It is suggested that the active species for formaldehyde formation is well dispersed molybdenum oxide clusters on SiO₂ support: the optimum dispersion of the clusters affords the highest activity for formaldehyde formation.     

Selective oxidation of methane with air over silica catalysts

Partial oxidation of methane by oxygen to form formaldehyde, carbon oxides, and C₂ products (ethane and ethene) has been studied over silica catalyst supports (fumed Cabosil and Grace 636 silica gel) in the 630–780 °C temperature range under ambient pressure. The silica catalysts exhibit high space time yields (at low conversions) for methane partial oxidation to formaldehyde, and the C₂ hydrocarbons were found to be parallel products with formaldehyde. Short residence times enhanced both the C₂ hydrocarbons and formaldehyde selectivities over the carbon oxides even within the differential reactor regime at 780 °C. This suggests that the formaldehyde did not originate from methyl radicals, but rather from methoxy complexes formed upon the direct chemisorption of methane at the silica surface at high temperature. Very high formaldehyde space time yields (e.g., 812 g/kg cat h at the gas hourly space velocity = 560 000 (NTP)/kg cat h) could be obtained over the silica gel catalyst at 780 °C with a methane/air mixture of 1.5/1. These yields greatly surpass those reported for silicas earlier, as well as those over many other catalysts. Low CO₂ yields were observed under these reaction conditions, and the selectivities to formaldehyde and C₂ hydrocarbons were 28.0 and 38.8%, respectively, at a methane conversion of 0.7%. A reaction mechanism was proposed for the methane activation over the silica surface based on the present studies, which can explain the product distribution patterns (specifically the parallel formation of formaldehyde and C₂ hydrocarbons).     

Study of new catalysts based on vanadium oxide supported on mesoporous silica for the partial oxidation of methane to formaldehyde: Catalytic properties and reaction mechanism

Vanadium oxide supported on mesoporous silica has been synthesized by a novel method and the resulting species tested as catalysts for the partial oxidation of methane to formaldehyde at atmospheric pressure. These catalysts appear to be very active and selective toward formaldehyde. Space–time yields superior to those of all known catalysts of the same type have been obtained. Kinetic parameters all tend to show that the same mechanism postulated for supported vanadium catalyst is taking place. The positive effect of water is also seen. The high performance has been attributed to the wide dispersion of vanadium-isolated species, which are known to be very active and selective, and to greatly superior silanol surface content than in other catalysts. The novel preparation method favors the formation of given isolated species that will be the most active and selective.     

Heat transport limitations and reaction scheme of partial oxidation of methane to synthesis gas over supported rhodium catalysts

The partial oxidation of methane to synthesis gas over supported Rh catalysts is investigated, paying particular attention to removing heat transport limitations and identifying the reaction conditions within the kinetic-controlling regime. The results obtained suggest that the reaction follows the sequence of total oxidation to CO₂ and H₂O, followed by reforming reactions to synthesis gas.     

Transient response of catalyst bed temperature in the pulsed reaction of partial oxidation of methane to synthesis gas over supported group VIII metal catalysts

Mechanisms of partial oxidation of methane to synthesis gas were studied using a pulsed reaction technique and temperature jump measurement. Catalyst bed temperatures were directly measured by introducing 1 and 3 ml pulses of a mixture of CH₄ and O₂ (2/1). With Ir, Pt and Ni/TiO₂ catalysts, a sudden temperature increase at the front edge of the catalyst bed was observed upon introduction of the pulse. The synthesis gas production basically proceeded via two-step paths consisting of highly exothermic complete methane oxidation to give H₂O and CO₂, followed by the endothermic reforming of methane with H₂O and CO₂. In contrast, with the Rh and Pd/TiO₂ catalysts, the temperature at the front edge of the catalyst bed decreased upon introduction of the CH₄/O₂ (2/1) pulse and a small increase in the temperature at the rear end was observed. Initially, the endothermic decomposition of CH₄ to H₂ and deposited carbon or CH_x probably took place at the front edge of the catalyst bed, after which the deposited carbon or generated CH_x species would be oxidized into CO_x. When the Ru/TiO₂ catalyst was used, a temperature increase at the front edge of the catalyst bed was observed upon introduction of the 3 ml pulse of CH₄/O₂. In contrast, the temperature drop at the front edge of the catalyst bed was observed for a 1 ml pulse of CH₄/O₂. These results seemed to exhibit two possibilities for a synthesis gas formation route over the Ru/TiO₂ catalyst. The reaction pathway of the partial oxidation of methane with group VIII metal-loaded catalysts depended strongly upon the metal species and reaction conditions.     

Reaction mechanism of partial oxidation of methane to synthesis gas over supported ni catalysts

A mechanistic study on the partial oxidation of methane to synthesis gas (H₂ and CO) was conducted with supported nickel catalysts. To investigate the reaction mechanism, pulse experiments, O₂-TPD, and a comparison of the moles of reactants and products were carried out. From the O₂-TPD experiment, it was observed that the active catalyst in the synthesis gas production desorbed oxygen at a lower temperature. In the pulse experiment, the temperature of the top of the catalyst bed increased with the pulses, whereas the temperature of the bottom decreased. This suggests that there are two kinds of reactions, that is, the total oxidation of methane (exothermic) at the top and reforming reactions (endothermic) at the bottom. From the comparison of the moles of reactants and products, it was found that the moles of CO₂, CH₄ and H₂O decreased as the moles of H₂ and CO increased. The results support the mechanism that synthesis gas is produced through a two-step reaction mechanism: the total oxidation of methane to CO₂ and H₂O takes place first, followed by the reforming reaction of the produced CO₂ and H₂O with residual CH₄ to form synthesis gas. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Pulse study of methane partial oxidation to syngas over SiO2-supported nickel catalysts

Methane was pulsed over pure CuO and NiO as well as Cu/La₂O₃ and Ni/La₂O₃ catalysts at 600° C. Results indicate that the mechanisms for methane activation over copper and nickel are quite different. Over CuO, methane is converted to CO₂ and H₂O, most likely via the combustion mechanism; whereas metallic copper does not activate methane. Over NiO in the presence of metallic nickel sites, methane activation follows the pyrolysis mechanism to give CO, CO₂, H₂ and H₂O. Similar results were obtained over the Cu/La₂O₃ and Ni/La₂O₃ catalysts. XRD investigations indicate that copper and nickel existed as CuLa₂O₄ and LaNiO₃ respectively in the La₂O₃-supported catalysts. The effect of La₂O₃ on the activation of methane is discussed.     

Mechanistic study of partial oxidation of methane to synthesis gas over supported rhodium and ruthenium catalysts using in situ time-resolved FTIR spectroscopy

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane to synthesis gas and the interaction of CH₄/O₂/He (2/1/45) gas mixture with adsorbed CO species over SiO₂ and γ-Al₂O₃ supported Rh and Ru catalysts at 500–600°C. It was found that CO is the primary product for the reaction of CH₄/O₂/He (2/1/45) gas mixture over H₂ reduced and working state Rh/SiO₂ catalyst. Direct oxidation of methane is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product for the reaction of CH₄/O₂/He (2/1/45) gas mixture over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway of CO formation over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts is via the reforming reactions of CH₄ with CO₂ and H₂O. The effect of space velocity on the partial oxidation of methane over SiO₂ and γ-Al₂O₃ supported Rh and Ru catalysts is consistent with the above mechanisms. It is also found that consecutive oxidation of surface CO species is an important pathway of CO₂ formation during the partial oxidation of methane to synthesis gas over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts.     

A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts

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.     

Partial oxidation of methane over ruthenium catalysts

The catalytic partial oxidation of methane with oxygen to produce synthesis gas was studied under a wide range of conditions over supported ruthenium catalysts. The microreador results demonstrated the high activity of ruthenium catalysts for this reaction. A catalyst having as little as 0.015% (w/w) Ru on Al₂O₃ gave a higher synthesis gas selectivity than a catalyst having 5% Ni on SiO₂. XANES measurements for fresh and used catalyst samples confirmed that ruthenium is reduced from ruthenium dioxide to ruthenium metal early during the experiments. Ruthenium metal is thus the active element for the methane partial oxidation reaction.     

Propane partial oxidation to acrolein over combined catalysts

A novel approach for the partial oxidation of propane to acrolein, based on the use of layers of combined catalysts in a single reactor, provides good yields of acrolein with selectivity above 62%. The results depend strongly on the layer configuration, and reveal new mechanistic features for the process. This revised version was published online in August 2006 with corrections to the Cover Date.     

Selective oxidation of methane to CO and H2 over unreduced NiO-rare earth oxide catalysts

NiO-LnO _x (Ln = lanthanide) catalysts (with NiLn=11) without prereduction show high activity/selectivity and very high productivity in the oxidative conversion of methane to CO and H₂. The catalysts are first activated in the initial reaction, which is started at 535–560°C, by the reduction of NiO and creation of active sites. The carbon deposition on the catalysts in the reaction, particularly for the NiO-Gd₂O₃, NiO-Tb₄O₇ and NiO-Dy₂O₃ catalysts, is quite fast but it has caused a little or no influence on the catalytic activity/selectivity. Pulse reaction of pure methane on NiO-Nd₂O₃ (at 600°C) shows involvement of lattice oxygen in the initial reaction and also reveals formation of carbon from CO on the catalyst reduced in the reaction.     

Transient kinetics of toluene partial oxidation over V/Ti oxide catalysts

Transient kinetics in the toluene oxidation over V/Ti oxide catalysts prepared by grafting and impregnation have been compared. V⁴⁺ cations are supposed to be the sites for the formation of electrophilic oxygen species participating in deep oxidation. Another oxygen species (probably nucleophilic) present on the oxidised catalyst surface are responsible for benzaldehyde formation. Selectivity of 80–100% can be obtained during the initial period of the reaction on the grafted catalysts in the presence of gaseous oxygen and during the interaction of toluene (without O₂ in the mixture) with partially reduced catalysts.     

FTIR spectroscopic investigation of the active sites on different types of silica catalysts for methane partial oxidation to formaldehyde

Several commercial silica samples showing different catalytic activities in the partial oxidation of methane (MPO) to formaldehyde have been investigated using FTIR technique. Two IR absorption bands at 893 and 909 cm^–1, observed upon dehydroxylation of the silica catalysts and assigned to reactive siloxane sites on the surface (strained siloxane bridges), were found to disappear upon heating in methane at high temperature. The catalytic activity increases together with the intensity of the bands due to such strained sites in the different SiO₂ samples.     

Partial oxidation of methane to synthesis gas over Rh-hexaaluminate-based catalysts

The partial oxidation of methane to synthesis gas over catalysts consisting of Rh supported on hexaaluminates (BaAl₁₂O₁₉, CaAl₁₂O₁₉ and SrAl₁₂O₁₉) was investigated at atmospheric pressure and high reactant dilution in order to compare their performances within the kinetic-controlling regime. Comparison with the results obtained over a commercial Rh/-Al₂O₃ system indicates that hexaaluminate catalysts are active and selective in this reaction. Despite of the higher surface area of the support, hexaaluminate-supported catalysts were found less stable, active and selective than an -Al₂O₃-supported catalyst.     

Combined catalytic partial oxidation and CO2 reforming of methane over supported cobalt catalysts

The combined partial oxidation and CO₂ reforming of methane to synthesis gas was investigated over the reduced Co/MgO, Co/CaO, and Co/SiO₂ catalysts. Only Co/MgO has proved to be a highly efficient and stable catalyst. It provided about 94–95% yields to H₂ and CO at the high space velocity of 105000 mlg^–1h^–1 and for feed ratios CH₄/CO₂/O₂=4/2/1, without any deactivation for a period of study of 110 h. In contrast, the reduced Co/CaO and Co/SiO₂ provided no activity for the formation of H₂ and CO. The structure and reducibility of the calcined catalysts were examined using X-ray diffraction and temperature-programmed reduction, respectively. A solid solution of CoO and MgO, which was difficult to reduce, was identified in the 800°C calcined MgO-supported catalyst. The strong interactions induced by the formation of the solid solution are responsible for its superior activity in the combined reaction. The effects of reaction temperature, space velocity, and O₂/CO₂ ratio in the feed gases (while keeping the C/O ratio constant at 1/1) were investigated over the Co/MgO catalyst. The H₂/CO ratio in the product of the combined reaction increased with increasing O₂/CO₂ ratio in the feed.     

An investigation on the reaction mechanism for the partial oxidation of methane to synthesis gas over platinum

The partial oxidation of methane to synthesis gas has been investigated by admitting pulses of pure methane, pure oxygen and mixtures of methane and oxygen to platinum sponge at temperatures ranging from 973 to 1073 K. On reduced platinum the decomposition of methane results in the formation of surface carbon and hydrogen. No deposition of carbon occurs during the interaction of methane with a partly oxidised catalyst. Oxygen is present in three different forms under the conditions studied: platinum oxide, dissolved oxygen and chemisorbed oxygen species. Carbon monoxide and hydrogen are produced directly from methane via oxygen present as platinum oxide. Activation of methane involving dissolved oxygen provides a parallel route to carbon dioxide and water. Both platinum oxide and chemisorbed oxygen species are involved in the oxidation of carbon monoxide and hydrogen. In the presence of both methane and dioxygen at a stoichiometric feed ratio the dominant pathways are the direct formation of CO and H₂ followed by their consecutive oxidation. A Mars-van Krevelen redox cycle is postulated for the partial oxidation of methane: the oxidation of methane is accompanied by the reduction of platinum oxide, which is reoxidised by incorporation of dioxygen into the catalyst.     

Supported nanocomposite catalysts for high-temperature partial oxidation of methane

In order to utilize the vast potential of nanoparticles for industrial catalysis, it is necessary to develop methods to stabilize these particles at realistic technical conditions and to formulate nanoparticle-based catalysts in a way that facilitates handling and reduces health and safety concerns. We have previously demonstrated that metal nanoparticles can be efficiently stabilized by embedding them into a high-temperature stable nanocomposite structure. Building onto these results, we report here on the next step towards a simple, hierarchically structured catalyst via supporting platinum barium-hexaaluminate (Pt-BHA) nanocomposites onto a range of different conventional and novel support structures (monoliths, foams, and felts). The catalysts were characterized via SEM, TEM, XRD, porosimetry, chemisorption, and reactive tests in catalytic partial oxidation of methane to synthesis gas (CPOM), and compared to conventionally prepared Pt-catalysts. In particular silica felt supported Pt-BHA showed excellent activity and selectivity combined with good stability and very low noble metal requirement at the demanding high-temperature conditions of short-contact time CPOM. Overall, we see great potential for these supported nanocomposite catalysts for use in demanding environments, such as high-temperature, high-throughput conditions in fuel processing and similar energy-related applications.     

Low temperature oxidative conversion of methane to synthesis gas over Co/rare earth oxide catalysts

CoO-rare earth oxide catalysts (particularly CoO-Yb₂O₃) show high activity and selectivity in the oxidative conversion of methane to CO and H₂ with very high productivity at low temperatures ( 700 °C as low as 300 °C).     

Mechanism of the partial oxidation of methane to synthesis gas over Pd

The partial oxidation of methane to synthesis gas has been studied in an isothermal continuous flow reactor operated with the phases in plug flow, using a silica-supported palladium catalyst. The reaction mechanism involves the sequential combustion and reforming of methane. The catalyst bed is not uniform in terms of the composition of the palladium phase. The implications for investigations using a pulse apparatus are discussed. Finally, large palladium crystallites readily grow carbon filaments. This revised version was published online in July 2006 with corrections to the Cover Date.