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.

A comparison of two models for the vibration response of piled foundations to inertial and underground-railway-induced loadings

The vibration response of piled foundations due to ground-borne vibration produced by an underground railway is a largely-neglected area in the field of structural dynamics. However, this continues to be an important aspect of research as it is expected that the presence of piled foundations can have a significant influence on the propagation and transmission of the wavefield produced by the underground railway. This paper presents a comparison of two methods that can be employed in calculating the vibration response of a piled foundation: an efficient semi-analytical model, and a Boundary Element model. The semi-analytical model uses a column or an Euler beam to model the pile, and the soil is modelled as a linear, elastic continuum that has the geometry of a thick-walled cylinder with an infinite outer radius and an inner radius equal to the radius of the pile. The boundary element model uses a constant-element BEM formulation for the halfspace, and a rectangular discretisation of the circular pile-soil interface. The piles are modelled as Timoshenko beams. Pile-soil-pile interactions are inherently accounted for in the BEM equations, whereas in the semi-analytical model these are quantified using the superposition of interaction factors. Both models use the method of joining subsystems to incorporate the incident wavefield generated by the underground railway into the pile model. Results are computed for a single pile subject to an inertial loading, pile-soil-pile interactions, and a pile group subjected to excitation from an underground railway. The two models are compared in terms of accuracy, computation time, versatility and applicability, and guidelines for future vibration prediction models involving piled foundations are proposed.