The attrition behaviour of oxygen-carriers under inert and reacting conditions

The attrition of two potential oxygen-carriers for chemical-looping, 100. wt% mechanically-mixed, unsupported iron oxide (400-600 μm diameter) and 25. wt% copper oxide impregnated on alumina (600-900 μm diameter), has been studied. The rates of attrition of batches of these particles whilst they were being fluidised and subjected to successive cycles of reduction and oxidation were determined by measuring the rate of production of fine particles elutriated from the bed, as well as progressive changes in the distribution of particle sizes retained in the bed. The ability of the particles to withstand impacts was also investigated by examining the degree of fragmentation of 1. g of reacted particles of known size on projecting them at a target at various velocities. It was found that the mechanical strength of the iron oxide particles deteriorated significantly after repeated cycles of oxidation and reduction. Thus, the rate of elutriation increased ~35-fold between the 1st and 10th cycle. At an impact velocity of 38. m/s, the amount of fragmentation in the impact test, viz. mass fraction of particles after impact having a size less than that before impact, increased from ~2.3. wt% (fresh particles) to 98. wt% after the 10th cycle. The CuO particles, in comparison, were able to withstand repeated reaction: no signs of increased rates of elutriation or fragmentation were observed over ten cycles. These results highlight the importance of selecting a durable support for oxygen-carriers. © 2011 Elsevier Ltd.

Steady-state modelling of the universal exhaust gas oxygen (UEGO) sensor

The universal exhaust gas oxygen (UEGO) sensor is a well-established device which was developed for the measurement of relative air fuel ratio in internal combustion engines. There is, however, little information available which allows for the prediction of the UEGO's behaviour when exposed to arbitrary gas mixtures, pressures and temperatures. Here we present a steady-state model for the sensor, based on a solution of the Stefan-Maxwell equation, and which includes a momentum balance. The response of the sensor is dominated by a diffusion barrier, which controls the rate of diffusion of gas species between the exhaust and a cavity. Determination of the diffusion barrier characteristics, especially the mean pore size, porosity and tortuosity, is essential for the purposes of modelling, and a measurement technique based on identification of the sensor pressure giving zero temperature sensitivity is shown to be a convenient method of achieving this. The model, suitably calibrated, is shown to make good predictions of sensor behaviour for large variations of pressure, temperature and gas composition. © 2012 IOP Publishing Ltd.

Electron spin resonance signature of the oxygen vacancy in HfO 2

The oxygen vacancy has been inferred to be the critical defect in HfO 2, responsible for charge trapping, gate threshold voltage instability, and Fermi level pinning for high work function gates, but it has never been conclusively identified. Here, the electron spin resonance g tensor parameters of the oxygen vacancy are calculated, using methods that do not over-estimate the delocalization of the defect wave function, to be g xx = 1.918, g yy = 1.926, g zz = 1.944, and are consistent with an observed spectrum. The defect undergoes a symmetry lowering polaron distortion to be localized mainly on a single adjacent Hf ion. © 2012 American Institute of Physics.

A high performance oxygen storage material for chemical looping processes with CO2 capture

Chemical looping combustion (CLC) is a novel combustion technology that involves cyclic reduction and oxidation of oxygen storage materials to provide oxygen for the combustion of fuels to CO2 and H2O, whilst giving a pure stream of CO2 suitable for sequestration or utilisation. Here, we report a method for preparing of oxygen storage materials from layered double hydroxides (LDHs) precursors and demonstrate their applications in the CLC process. The LDHs precursor enables homogeneous mixing of elements at the molecular level, giving a high degree of dispersion and high-loading of active metal oxide in the support after calcination. Using a Cu-Al LDH precursor as a prototype, we demonstrate that rational design of oxygen storage materials by material chemistry significantly improved the reactivity and stability in the high temperature redox cycles. We discovered that the presence of sodium-containing species were effective in inhibiting the formation of copper aluminates (CuAl2O4 or CuAlO 2) and stabilising the copper phase in an amorphous support over multiple redox cycles. A representative nanostructured Cu-based oxygen storage material derived from the LDH precursor showed stable gaseous O2 release capacity (∼5 wt%), stable oxygen storage capacity (∼12 wt%), and stable reaction rates during reversible phase changes between CuO-Cu 2O-Cu at high temperatures (800-1000 °C). We anticipate that the strategy can be extended to manufacture a variety of metal oxide composites for applications in novel high temperature looping cycles for clean energy production and CO2 capture. © The Royal Society of Chemistry 2013.

Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion

Chemical looping combustion (CLC) uses a metal oxide (the oxygen carrier) to provide oxygen for the combustion of a fuel and gives an inherent separation of pure CO2 with minimal energy penalty. In solid-fuel CLC, volatile matter will interact with oxygen carriers. Here, the interaction between iron-based oxygen carriers and a volatile hydrocarbon (n-heptane) was investigated in both a laboratory-scale fluidised bed and a thermogravimetric analyser (TGA). Experiments were undertaken to characterise the thermal decomposition of the n-heptane occurring in the presence and in the absence of the oxygen carrier. In a bed of inert particles, carbon deposition increased with temperature and acetylene appeared as a possible precursor. For a bed of carrier consisting of pure Fe2O3, carbon deposition occurred once the Fe2O3 was fully reduced to Fe. When the Fe2O3 was doped with 10 mol % Al2O3 (Fe90Al), deposition started when the carrier was reduced to a mixture of Fe and FeAl2O4, the latter being very unreactive. Furthermore, when pure Fe2O3 was fully reduced to Fe, agglomeration of the fluidised bed occurred. However, Fe90Al did not give agglomeration even after extended reduction. The results suggest that Fe90Al is promising for the CLC of solid fuels. © 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Creep and oxygen diffusion in magnetite

The creep rate of polycrystalline Fe3O4 has been measured as a fonction of stress and oxygen partial pressure in the temperature range 480-1100°C. A regime of power law creep is found at high stress, with a stress exponent of ≈- 3.1 and an activation energy of 264 kJ/mol. A regime of diffusional flow is found at lower stresses and is interpreted as Nabarro-Herring creep. The data for the two regimes are combined to deduce an oxygen diffusion coefficient of ≈-10-5 exp(-264 kJ/mol/RT) m2s-1, with oxygen vacancies suggested as the mobile species. © 1990.

Oxygen carrier dispersion in inert packed beds to improve performance in chemical looping combustion

Various packed beds of copper-based oxygen carriers (CuO on Al2O3) were tested over 100 cycles of low temperature (673K) Chemical Looping Combustion (CLC) with H2 as the fuel gas. The oxygen carriers were uniformly mixed with alumina (Al2O3) in order to investigate the level of separation necessary to prevent agglomeration. It was found that a mass ratio of 1:6 oxygen carrier to alumina gave the best performance in terms of stable, repeating hydrogen breakthrough curves over 100 cycles. In order to quantify the average separation achieved in the mixed packed beds, two sphere-packing models were developed. The hexagonal close-packing model assumed a uniform spherical packing structure, and based the separation calculations on a hypergeometric probability distribution. The more computationally intensive full-scale model used discrete element modelling to simulate random packing arrangements governed by gravity and contact dynamics. Both models predicted that average 'nearest neighbour' particle separation drops to near zero for oxygen carrier mass fractions of x≥0.25. For the packed bed systems studied, agglomeration was observed when the mass fraction of oxygen carrier was above this threshold. © 2013 Elsevier B.V.

Band gap opening of graphene after UV/ozone and oxygen plasma treatments

Graphene grown by Chemical Vapor Deposition (CVD) on nickel subsrate is oxidized by means of oxygen plasma and UV/Ozone treatments to introduce bandgap opening in graphene. The degree of band gap opening is proportional to the degree of oxidation on the graphene. This result is analyzed and confirmed by Scanning Tunnelling Microscopy/Spectroscopy and Raman spectroscopy measurements. Compared to conventional wet-oxidation methods, oxygen plasma and UV/Ozone treatments do not require harsh chemicals to perform, allow faster oxidation rates, and enable site-specific oxidation. These features make oxygen plasma and UV/Ozone treatments ideal candidates to be implemented in high-throughput fabrication of graphene-based microelectronics. © 2011 Materials Research Society.

CO2-gasification of a lignite coal in the presence of an iron-based oxygen carrier for chemical-looping combustion

Chemical-looping combustion (CLC) has the inherent property of separating the product 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. All techniques so far proposed for chemical looping with solid fuels involve initially the gasification of the solid fuel in order for the gaseous products to react with the oxygen carrier. Here, the rates of gasification of coal were compared when gasification was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. This enabled an examination of the ability of chemical looping materials to enhance the rate of gasification of solid fuels. Batch gasification and chemical-looping combustion experiments with a German lignite and its char are reported, using an electrically-heated fluidised bed reactor at temperatures from 1073 to 1223 K. The fluidising gas was CO2 in nitrogen. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. A numerical model was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at about 20% conversion when (i) the surface area for reaction was at its maximum and (ii) because of the accompanying increase in porosity and pore size, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle. Excellent agreement was observed between the rates predicted by the numerical model and those observed experimentally. ©2013 Elsevier Ltd. All rights reserved.

Oxygen vacancy defects in Ta2O5 showing long-range atomic re-arrangements

The structure, formation energy, and energy levels of the various oxygen vacancies in Ta2O5 have been calculated using the λ phase model. The intra-layer vacancies give rise to unusual, long-range bonding rearrangements, which are different for each defect charge state. The 2-fold coordinated intra-layer vacancy is the lowest cost vacancy and forms a deep level 1.5 eV below the conduction band edge. The 3-fold intra-layer vacancy and the 2-fold inter-layer vacancy are higher cost defects, and form shallower levels. The unusual bonding rearrangements lead to low oxygen migration barriers, which are useful for resistive random access memory applications. © 2014 AIP Publishing LLC.

Application of fast oxygen sensors for investigations into air-path dynamics and EGR distribution in a diesel engine

The control of NOX emissions by exhaust gas recirculation (EGR) is of widespread application. However, despite dramatic improvements in all aspects of engine control, the subtle mixing processes that determine the cylinder-to-cylinder distribution of the recirculated gas often results in a mal-distribution that is still an issue for the engine designer and calibrator. In this paper we demonstrate the application of a relatively straightforward technique for the measurement of the absolute and relative dilution quantity in both steady state and transient operation. This was achieved by the use of oxygen sensors based on standard UEGO (universal exhaust gas oxygen) sensors but packaged so as to give good frequency response (∼ 10 ms time constant) and be completely insensitivity to the sample pressure and temperature. Measurements can be made at almost any location of interest, for example exhaust and inlet manifolds as well as EGR path(s), with virtually no flow disturbance. At the same time, the measurements yield insights into air-path dynamics. We argue that "dilution", as indicated by the deviation of the oxygen concentration from that of air, is a more appropriate parameter than EGR rate in the context of NOX control, especially for diesel engines. Experimental results are presented for the EGR distribution in a current production light duty 4-cylinder diesel engine in which significant differences were found in the proportion of the recirculated gas that reached each cylinder. Even the individual inlet runners of the cylinders exhibited very different dilution rates - differences of nearly 50% were observed at some conditions. An application of such data may be in the improvement of calibration and validation of CFD and other modelling techniques. Copyright © 2014 SAE International.