Different methods of manufacturing FE-based oxygen carrier particles for reforming via chemical looping, and their effect on performance

Chemical looping combustion (CLC) is a means of combusting carbonaceous fuels, which inherently separates the greenhouse gas carbon dioxide from the remaining combustion products, and has the potential to be used for the production of high-purity hydrogen. Iron-based oxygen carriers for CLC have been subject to considerable work; however, there are issues regarding the lifespan of iron-based oxygen carriers over repeated cycles. In this work, haematite (Fe2O3) was reduced in an N2+CO+CO2 mixture within a fluidised bed at 850°C, and oxidised back to magnetite (Fe3O4) in a H2O+N2 mixture, with the subsequent yield of hydrogen during oxidation being of interest. Subsequent cycles started from Fe3O4 and two transition regimes were studied; Fe3O4↔Fe0.947O and Fe 3O4↔Fe. Particles were produced by mechanical mixing and co-precipitation. In the case of co-precipitated particles, Al was added such that the ratio of Fe:Al by weight was 9:1, and the final pH of the particles during precipitation was investigated for its subsequent effect on reactivity. This paper shows that co-precipitated particles containing additives such as Al may be able to achieve consistently high H2 yields when cycling between Fe3O4 and Fe, and that these yields are a function of the ratio of [CO2] to [CO] during reduction, where thermodynamic arguments suggest that the yield should be independent of this ratio. A striking feature with our materials was that particles made by mechanical mixing performed much better than those made by co-precipitation when cycling between Fe3O4 and Fe0.947O, but much worse than co-precipitated particles when cycling between Fe3O 4 and Fe.

Plasma enhanced chemical vapour deposition carbon nanotubes/nanofibres - How uniform do they grow?

The ability to grow carbon nanotubes/nanofibres (CNs) with a high degree of uniformity is desirable in many applications. In this paper, the structural uniformity of CNs produced by plasma enhanced chemical vapour deposition is evaluated for field emission applications. When single isolated CNs were deposited using this technology, the structures exhibited remarkable uniformity in terms of diameter and height (standard deviations were 4.1 and 6.3% respectively of the average diameter and height). The lithographic conditions to achieve a high yield of single CNs are also discussed. Using the height and diameter uniformity statistics, we show that it is indeed possible to accurately predict the average field enhancement factor and the distribution of enhancement factors of the structures, which was confirmed by electrical emission measurements on individual CNs in an array.

Plasma enhanced chemical vapour deposited carbon nanotubes for field emission applications

Plasma Enhanced Chemical Vapour Deposition is an extremely versatile technique for directly growing multiwalled carbon nanotubes onto various substrates. We will demonstrate the deposition of vertically aligned nanotube arrays, sparsely or densely populated nanotube forests, and precisely patterned arrays of nanotubes. The high-aspect ratio nanotubes (∼50 nm in diameter and 5 microns long) produced are metallic in nature and direct contact electrical measurements reveal that each nanotube has a current carrying capacity of 107-108 A/cm2, making them excellent candidates as field emission sources. We examined the field emission characteristics of dense nanotube forests as well as sparse nanotube forests and found that the sparse forests had significantly lower turn-on fields and higher emission currents. This is due to a reduction in the field enhancement of the nanotubes due to electric field shielding from adjacent nanotubes in the dense nanotube arrays. We thus fabricated a uniform array of single nanotubes to attempt to overcome these issues and will present the field emission characteristics of this.

Electrical and field emission investigation of individual carbon nanotubes from plasma enhanced chemical vapour deposition

Plasma enhanced chemical vapour deposition (PECVD) is a controlled technique for the production of vertically aligned multiwall carbon nanotubes for field emission applications. In this paper, we investigate the electrical properties of individual carbon nanotubes which is important for designing field emission devices. PECVD nanotubes exhibit a room temperature resistance of 1-10 kΩ/μm length (resistivity 10-6 to 10-5 Ω m) and have a maximum current carrying capability of 0.2-2 mA (current density 107-108 A/cm2). The field emission characteristics show that the field enhancement of the structures is strongly related to the geometry (height/radius) of the structures and maximum emission currents of ∼ 10 μA were obtained. The failure of nanotubes under field emission is also discussed. © 2002 Elsevier Science B.V. All rights reserved.

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.