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.

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.

Near-complete transuranic waste incineration in a thorium fuelled pressurised water reactor

The production of long-lived transuranic (TRU) waste is a major disadvantage of fission-based nuclear power. Incineration, and virtual elimination, of waste stockpiles is possible in a thorium (Th) fuelled critical or subcritical fast reactor. Fuel cycles producing a net decrease in TRUs are possible in conventional pressurised water reactors (PWRs). However, minor actinides (MAs) have a detrimental effect on reactivity and stability, ultimately limiting the quality and quantity of waste that can be incinerated. In this paper, we propose using a thorium-retained-actinides fuel cycle in PWRs, where the reactor is fuelled with a mixture of thorium and TRU waste, and after discharge all actinides are reprocessed and returned to the reactor. To investigate the feasibility and performance of this fuel cycle an assembly-level analysis for a one-batch reloading strategy was completed over 125 years of operation using WIMS 9. This one-batch analysis was performed for simplicity, but allowed an indicative assessment of the performance of a four-batch fuel management strategy. The build-up of 233U in the reactor allowed continued reactive and stable operation, until all significant actinide populations had reached pseudo-equilibrium in the reactor. It was therefore possible to achieve near-complete transuranic waste incineration, even for fuels with significant MA content. The average incineration rate was initially around 330 kg per GW th year and tended towards 250 kg per GW th year over several decades: a performance comparable to that achieved in a fast reactor. Using multiple batch fuel management, competitive or improved end-of-cycle burn-up appears achievable. The void coefficient (VC), moderator temperature coefficient (MTC) and Doppler coefficient remained negative. The quantity of soluble boron required for a fixed fuel cycle length was comparable to that for enriched uranium fuel, and acceptable amounts can be added without causing a positive VC or MTC. This analysis is limited by the consideration of a single fuel assembly, and it will be necessary to perform a full core coupled neutronic-thermal-hydraulic analysis to determine if the design in its current form is feasible. In particular, the potential for positive VCs if the core is highly or locally voided is a cause for concern. However, these results provide a compelling case for further work on concept feasibility and fuel management, which is in progress. © 2011 Elsevier Ltd. All rights reserved.

The performance of closed reactor grade plutonium-thorium fuel cycles in reduced-moderation pressurised water reactors

The production of long-lived transuranic (TRU) waste is a major disadvantage of fission-based nuclear power. Previous work has indicated that TRU waste can be virtually eliminated in a pressurised water reactor (PWR) fuelled with a mixture of thorium and TRU waste, when all actinides are returned to the reactor after reprocessing. However, the optimal configuration for a fuel assembly operating this fuel cycle is likely to differ from the current configuration. In this paper, the differences in performance obtained in a reduced-moderation PWR operating this fuel cycle were investigated using WIMS. The chosen configuration allowed an increase of at least 20% in attainable burn-up for a given TRU enrichment. This will be especially important if the practical limit on TRU enrichment is low. The moderator reactivity coefficients limit the enrichment possible in the reactor, and this limit is particularly severe if a negative void coefficient is required for a fully voided core. Several strategies have been identified to mitigate this. Specifically, the control system should be designed to avoid a detrimental effect on moderator reactivity coefficients. The economic viability of this concept is likely to be dependent on the achievable thermal-hydraulic operating conditions. © 2012 Elsevier Ltd. All rights reserved.

Accelerator-induced transients in Accelerator Driven Subcritical Reactors

Achieving higher particles energies and beam powers have long been the main focus of research in accelerator technology. Since Accelerator Driven Subcritical Reactors (ADSRs) have become the subject of increasing interest, accelerator reliability and modes of operation have become important matters that require further research and development in order to accommodate the engineering and economic needs of ADSRs. This paper focuses on neutronic and thermo-mechanical analyses of accelerator-induced transients in an ADSR. Such transients fall into three main categories: beam interruptions (trips), pulsed-beam operation, and beam overpower. The concept of a multiple-target ADSR is shown to increase system reliability and to mitigate the negative effects of beam interruptions, such as thermal cyclic fatigue in the fuel cladding and the huge financial cost of total power loss. This work also demonstrates the effectiveness of the temperature-to-reactivity feedback mechanisms in ADSRs. A comparison of shutdown mechanisms using control rods and beam cut-off highlights the intrinsic safety features of ADSRs. It is evident that the presence of control rods is crucial in an industrial-scale ADSR. This paper also proposes a method to monitor core reactivity online using the repetitive pattern of beam current fluctuations in a pulsed-beam operation mode. Results were produced using PTS-ADS, a computer code developed specifically to study the dynamic neutronic and thermal responses to beam transients in subcritical reactor systems. © 2012 Elsevier B.V.

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.

Thermal evolution of Er silicate thin films grown by rf magnetron sputtering

Stoichiometric Er silicate thin films, monosilicate (Er2SiO 5) and disilicate (Er2Si2O7), have been grown on c-Si substrates by rf magnetron sputtering. The influence of annealing temperature in the range 1000-1200 °C in oxidizing ambient (O 2) on the structural and optical properties has been studied. In spite of the known reactivity of rare earth silicates towards silicon, Rutherford backscattering spectrometry shows that undesired chemical reactions between the film and the substrate can be strongly limited by using rapid thermal treatments. Monosilicate and disilicate films crystallize at 1100 and 1200 °C, respectively, as shown by x-ray diffraction analysis; the crystalline structures have been identified in both cases. Moreover, photoluminescence (PL) measurements have demonstrated that the highest PL intensity is obtained for Er2Si2O7 film annealed at 1200 °C. In fact, this treatment allows us to reduce the defect density in the film, in particular by saturating oxygen vacancies, as also confirmed by the increase of the lifetime of the PL signal. © 2008 IOP Publishing Ltd.

Optical and structural properties of Er2O3 films grown by magnetron sputtering

The structural properties and the room temperature luminescence of Er 2O3 thin films deposited by magnetron sputtering have been studied. In spite of the well-known high reactivity of rare earth oxides towards silicon, films characterized by good morphological properties have been obtained by using a SiO2 interlayer between the film and the silicon substrate. The evolution of the properties of the Er2O3 films due to thermal annealing processes in oxygen ambient performed at temperatures in the range of 800-1200°C has been investigated in detail. The existence of well defined annealing conditions (rapid treatments at a temperature of 1100°C or higher) allowing to avoid the occurrence of extensive chemical reactions with the oxidized substrate has been demonstrated; under these conditions, the thermal process has a beneficial effect on both structural and optical properties of the film, and an increase of the photoluminescence (PL) intensity by about a factor of 40 with respect to the as-deposited material has been observed. The enhanced efficiency of the photon emission process has been correlated with the longer lifetime of the PL signal. Finally, the conditions leading to a reaction of Er2O3 with the substrate have been also identified, and evidences about the formation of silicate-like phases have been collected. © 2006 American Institute of Physics.

A genetically mediated bias in decision making driven by failure of amygdala control.

Genetic variation at the serotonin transporter-linked polymorphic region (5-HTTLPR) is associated with altered amygdala reactivity and lack of prefrontal regulatory control. Similar regions mediate decision-making biases driven by contextual cues and ambiguity, for example the "framing effect." We hypothesized that individuals hemozygous for the short (s) allele at the 5-HTTLPR would be more susceptible to framing. Participants, selected as homozygous for either the long (la) or s allele, performed a decision-making task where they made choices between receiving an amount of money for certain and taking a gamble. A strong bias was evident toward choosing the certain option when the option was phrased in terms of gains and toward gambling when the decision was phrased in terms of losses (the frame effect). Critically, this bias was significantly greater in the ss group compared with the lala group. In simultaneously acquired functional magnetic resonance imaging data, the ss group showed greater amygdala during choices made in accord, compared with those made counter to the frame, an effect not seen in the lala group. These differences were also mirrored by differences in anterior cingulate-amygdala coupling between the genotype groups during decision making. Specifically, lala participants showed increased coupling during choices made counter to, relative to those made in accord with, the frame, with no such effect evident in ss participants. These data suggest that genetically mediated differences in prefrontal-amygdala interactions underpin interindividual differences in economic decision making.

Confidence in beliefs about pain predicts expectancy effects on pain perception and anticipatory processing in right anterior insula.

Psychological factors play a major role in exacerbating chronic pain. Effective self-management of pain is often hindered by inaccurate beliefs about the nature of pain which lead to a high degree of emotional reactivity. Probabilistic models of perception state that greater confidence (certainty) in beliefs increases their influence on perception and behavior. In this study, we treat confidence as a metacognitive process dissociable from the content of belief. We hypothesized that confidence is associated with anticipatory activation of areas of the pain matrix involved with top-down modulation of pain. Healthy volunteers rated their beliefs about the emotional distress that experimental pain would cause, and separately rated their level of confidence in this belief. Confidence predicted the influence of anticipation cues on experienced pain. We measured brain activity during anticipation of pain using high-density EEG and used electromagnetic tomography to determine neural substrates of this effect. Confidence correlated with activity in right anterior insula, posterior midcingulate and inferior parietal cortices during the anticipation of pain. Activity in the right anterior insula predicted a greater influence of anticipation cues on pain perception, whereas activity in right inferior parietal cortex predicted a decreased influence of anticipatory cues. The results support probabilistic models of pain perception and suggest that confidence in beliefs is an important determinant of expectancy effects on pain perception.

Anxiety reduction through detachment: subjective, physiological, and neural effects.

The ability to volitionally regulate emotions helps to adapt behavior to changing environmental demands and can alleviate subjective distress. We show that a cognitive strategy of detachment attenuates subjective and physiological measures of anticipatory anxiety for pain and reduces reactivity to receipt of pain itself. Using functional magnetic resonance imaging, we locate the potential site and source of this modulation of anticipatory anxiety in the medial prefrontal/anterior cingulate and anterolateral prefrontal cortex, respectively.

Extent of oxidation of hydrocarbons desorbing from the lubricant oil layer in spark-ignition engines

The extent of oxidation of hydrocarbons desorbing from the oil layer has been measured directly in a hydrogen-fueled, spark-ignited engine in which the lubricant oil was doped with a single component hydrocarbon. The amount of hydrocarbon desorbed and oxidized could be measured simultaneously as the dopant was only source of carbon-containing species. The fraction oxidized was strongly dependent on engine load, hydrogen fuel-air ratio and dopant chemical reactivity, but only modestly dependent on spark timing and nitrogen dilution levels below 20 percent. Fast FID measurements at the cylinder exit showed that the surviving hydrocarbons emerge late in the exhaust stroke. © Copyright 1996 Society of Automotive Engineers, Inc.

Detailed design of242mAm breeding in pressurized water reactors

There is growing interest in the use of 242mAm as a nuclear fuel. Because of its very high thermal fission cross section and its large number of neutrons released per fission, it can be used for various unique applications, such as space propulsion, medical applications, and compact energy sources. Since the thermal absorption cross section of 242mAm is very high, the best way to obtain 242mAm is by the capture of fast or epithermal neutrons in 241Am. However, fast spectrum reactors are not readily available. In this paper, we explore the possibility of producing 242mAm in existing pressurized water reactors (PWRs) with minimal interference in reactor performance. As suggested in previous studies on the subject, the 242mAm breeding targets are shielded with strong thermal absorbers in order to suppress the thermal neutron flux that causes 242mAm destruction. Since 242mAm enrichment within the Am target mainly depends on the neutron energy distribution, which in turn depends on the Am target thickness and on the neutron filter cutoff energy (thermal absorber type), this unique Am target design was developed. In our study, Cd, Sm, and Gd were considered as thermal neutron filters, as suggested by Cesana et al. The most favorable results were obtained by irradiating Am targets covered either with Gd or Cd. In these cases, up to 8.65% enrichment of 242mAm is obtained after 4.5 yr (three successive PWR fuel cycles) of irradiation. It was also found that significant quantities [up to 1.3 kg/GW (electric)-yr] of 242mAm can be obtained in PWR reactors without notable interference with reactor performance. However, in order to maintain the original fuel cycle length, the enrichment of the driver (UO2) fuel must be increased by ∼1%, raised from the conventional 4.5 to 5.5%, depending on the thermal neutron filter used. The most important reactivity feedback coefficients for fuel assemblies containing the 242mAm breeding targets were evaluated and found to be close to those of a standard PWR. Another product of neutron capture in the 241Am reaction is 238Pu. It was found that in a typical 1000 MW (electric) PWR core with one-third of the fuel assemblies containing 241Am targets, up to 15.1 kg of 238Pu enriched to 80% can be produced per year.

HTGR fuel element depletion benchmark: Stage three results

Recently, a new numerical benchmark exercise for High Temperature Gas Cooled Reactor (HTGR) fuel depletion was defined. The purpose of this benchmark is to provide a comparison basis for different codes and methods applied to the burnup analysis of HTGRs. The benchmark specifications include three different models: (1) an infinite lattice of tristructural isotropic (TRISO) fuel particles, (2) an infinite lattice of fuel pebbles, and (3) a prismatic fuel including fuel and coolant channels. In this paper, we present the results of the third stage of the benchmark obtained with MCNP based depletion code BGCore and deterministic lattice code HELIOS 1.9. The depletion calculations were performed for three-dimensional model of prismatic fuel with explicitly described TRISO particles as well as for two-dimensional model, in which double heterogeneity of the TRISO particles was eliminated using reactivity equivalent physical transformation (RPT). Generally, good agreement in the results of the calculations obtained using different methods and codes was observed.

The potential use of 241Am as proliferation resistant burnable poison in PWRs

This paper discusses the use of 241Am as proliferation resistant burnable poison for light water reactors. Homogeneous addition of small (as little as 0.12%) amounts of 241Am to the conventional light water reactor fuel results in significant increase in 238Pu/Pu ratio in the discharged fuel improving its proliferation resistance. Moreover, 241Am, admixed to the fuel, acts as burnable absorber allowing for substantial reduction in conventional reactivity control means without a notable fuel cycle length penalty. This is possible due to favorable characteristics of 241Am transmutation chain. The fuel cycle length penalty of introducing 241Am into the core is evaluated and discussed, as well as the impact of He production in the fuel pins and degradation of reactivity feedback coefficients. Proliferation resistance and reactivity control features related to the use of 241Am are compared to those of using 237Np, which has also been suggested as an additive to the conventional fuel in order to improve its proliferation resistance. It was found that 241Am admixture is more favorable than 237Np admixture because of the smaller fuel cycle length penalty and higher burnable poison savings. Addition of either 237Np or 241Am would provide substantial but not ultimate protection from misuse of Pu originating in the spent fuel from the commercial power reactors. Therefore, the benefits from application of the concept would have to be carefully evaluated against the additional costs and proliferation risks associated with manufacturing of 237Np or 241Am doped fuel. Although this work concerns specifically with PWRs, the conclusions could also be applied to BWRs and, to some extent, to other thermal spectrum reactor types. © 2009 Elsevier Ltd. All rights reserved.