Partial oxidation

About: Partial oxidation is a research topic. Over the lifetime, 8261 publications have been published within this topic receiving 205069 citations.

Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions

Abstract: Oxidation is an important method for the synthesis of chemical intermediates in the manufacture of high-tonnage commodities, high-value fine chemicals, agrochemicals and pharmaceuticals: but oxidations are often inefficient. The introduction of catalytic systems using oxygen from air is preferred for 'green' processing. Gold catalysis is now showing potential in selective redox processes, particularly for alcohol oxidation and the direct synthesis of hydrogen peroxide. However, a major challenge that persists is the synthesis of an epoxide by the direct electrophilic addition of oxygen to an alkene. Although ethene is epoxidized efficiently using molecular oxygen with silver catalysts in a large-scale industrial process, this is unique because higher alkenes can only be effectively epoxidized using hydrogen peroxide, hydroperoxides or stoichiometric oxygen donors. Here we show that nanocrystalline gold catalysts can provide tunable active catalysts for the oxidation of alkenes using air, with exceptionally high selectivity to partial oxidation products ( approximately 98%) and significant conversions. Our finding significantly extends the discovery by Haruta that nanocrystalline gold can epoxidize alkenes when hydrogen is used to activate the molecular oxygen; in our case, no sacrificial reductant is needed. We anticipate that our finding will initiate attempts to understand more fully the mechanism of oxygen activation at gold surfaces, which might lead to commercial exploitation of the high redox activity of gold nanocrystals.

Partial oxidation of methane to synthesis gas using carbon dioxide

Abstract: INCREASING concern about world dependence on petroleum oil has generated interest in the more efficient use of natural gas1–4. The conversion of methane to the common feedstock synthesis gas (carbon monoxide and hydrogen) by steam reforming is already well established5, and we have shown recently that yields of syn-thesis gas in excess of 90% can be obtained at moderate tem-peratures and ambient pressure by partial oxidation, with air or oxygen, over supported transition-metal catalysts6,7. The use of carbon dioxide as an oxidant for conversion of natural gas to synthesis gas is well established in steam reforming5, and is also known in CO2 reforming (for example, the Calcor process8,9), in which the use of excess CO2 yields mainly CO. In the present work, we describe an alternative catalytic strategy for CO2 reform-ing which gives excellent yields (90%) from a stoichiometric (1:1) feed of CO2 and CH4. Carbon deposition ('coking'), which is a hazard of CO2-reforming routes, is suppressed here by the use of catalysts based on platinum-group metals. We show that the exothermic partial oxidation of CH2 and the endothermic CO2-reforming reaction can be carried out simultaneously, thus introducing the possibility of tuning the thermodynamics of the process.

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

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.