Kinetics of the chemical looping oxidation of H2 by a co-precipitated mixture of CuO and Al2O3

Chemical-looping combustion (CLC) has the inherent property of separating CO2 from flue gases. Instead of air, it uses an oxygen-carrier, usually in the form of a metal oxide, to provide oxygen for combustion. When used for the combustion of gaseous fuels, such as natural gas, or synthesis gas from the gasification of coal, the technique gives a stream of CO2 which, on an industrial scale, would be sufficiently pure for geological sequestration. An important issue is the form of the metal oxide, since it must retain its reactivity through many cycles of complete reduction and oxidation. Here, we report on the rates of oxidation of one constituent of synthesis gas, H2, by co-precipitated mixtures of CuO+Al2O3 using a laboratory-scale fluidised bed. To minimise the influence of external mass transfer, and also of errors in the measurement of [H2], particles sized to 355-500μm were used at low [H2], with the temperature ranging from 450 to 900°C. Under such conditions, the reaction was slow enough for meaningful measurements of the intrinsic kinetics to be made. The reaction was found to be first order with respect to H2. Above ∼800°C, the reaction of CuO was fast and conformed to the shrinking core mechanism, proceeding via the intermediate, Cu2O, in: 2CuO+H2→Cu2O+H2O, ΔH1073 K0=- 116.8 kJ/mol; Cu2O+H2→2Cu+H2O, ΔH1073 K0-80.9 kJ/mol. After oxidation of the products Cu and Cu2O back to CuO, the kinetics in subsequent cycles of chemical looping oxidation of H2 could be approximated by those in the first. Interestingly, the carrier was found to react at temperatures as low as 300°C. The influence of the number of cycles of reduction and oxidation is explored. Comparisons are drawn with previous work using reduction by CO. Finally, these results indicate that the kinetics of reaction of the oxygen carrier with gasifier synthesis gases is very much faster than rates of gasification of the original fuel. © 2010 The Institution of Chemical Engineers.

Non-catalytic multi-fuel reformer for syngas production for fuel cell applications

Rich combustion of n-heptane, diesel oil, jet A-1 kerosene, and bio-diesel (rapeseed-oil methyl ester) were studied to produce hydrogen enriched gas, ready for the cleanup stages for fuel cell applications. n-heptane was successfully reformed up to an equivalence ratio of 3:1, reaching a conversion efficiency up to 83% for a packed bed of alumina bead burner. Diesel, kerosene and bio-diesel were reformed to synthesis gas with conversion efficiency up to 65%. At equivalence ratio of 2:1 and P=7 kw, stability, low HC formation, high conversion efficiency, and low soot emission were achieved. A common synthesis gas composition around this condition was 15 and 13% H2, 15 and 17% CO, and 4 and 4.5% CO2 for n-heptane and diesel, jet A-1 and bio-diesel, respectively, for burner A. This is an abstract of a paper presented at the 2010 Spring National Meeting (San Antonio, TX 3/21-25/2010).

Gas-phase production of gold-decorated silica nanoparticles.

Gold-decorated silica nanoparticles were synthesized in a two-step process in which silica nanoparticles were produced by chemical vapor synthesis using tetraethylorthosilicate (TEOS) and subsequently decorated using two different gas-phase evaporative techniques. Both evaporative processes resulted in gold decoration of the silica particles. This study compares the mechanisms of particle decoration for a production method in which the gas and particles remain cool to a method in which the entire aerosol is heated. Results of transmission electron microscopy and visible spectroscopy studies indicate that both methods produce particles with similar morphologies and nearly identical absorption spectra, with peak absorption at 500-550 nm. A study of the thermal stability of the particles using heated-TEM indicates that the gold decoration on the particle surface remains stable at temperatures below 900 °C, above which the gold decoration begins to both evaporate and coalesce.

Growth kinetics and uniform scaling-up of graphene synthesis

Chemical vapor deposition on copper is the most widely used method to synthesize graphene at large scale. However, the clear understanding of the fundamental mechanisms that govern this synthesis is lacking. Using a vertical-flow, cold-wall reactor with short gas residence time we observe the early growths to study the kinetics of chemical vapor deposition of graphene on copper foils and demonstrate uniform synthesis at wafer scale. Our results indicate that the growth is limited by the catalytic dissociative dehydrogenation on the surface and copper sublimation hinders the graphene growth. We report an activation energy of 3.1 eV for ethylene-based graphene synthesis. © The Electrochemical Society.