An investigation of the kinetics of CO2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO2 at temperatures of ca. 750 °C of a synthetic sorbent composed of 15 wt% mayenite (Ca12Al14O33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation–calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model – the size distribution of grains – was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation.

A 5-step reduced mechanism for combustion of CO/H2/H2O/CH4/CO2 mixtures with low hydrogen/methane and high H2O content

In this study a 5-step reduced chemical kinetic mechanism involving nine species is developed for combustion of Blast Furnace Gas (BFG), a multi-component fuel containing CO/H2/CH4/CO2, typically with low hydrogen, methane and high water fractions, for conditions relevant for stationary gas-turbine combustion. This reduced mechanism is obtained from a 49-reaction skeletal mechanism which is a modified subset of GRI Mech 3.0. The skeletal and reduced mechanisms are validated for laminar flame speeds, ignition delay times and flame structure with available experimental data, and using computational results with a comprehensive set of elementary reactions. Overall, both the skeletal and reduced mechanisms show a very good agreement over a wide range of pressure, reactant temperature and fuel mixture composition. © 2012 The Combustion Institute..

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.

Ventilation effectiveness measures based on heat removal: Part 2. Application to natural ventilation flows

The three effectiveness measures based on the ability of a flow to flush buoyancy from a ventilated space proposed by Coffey and Hunt [Ventilation effectiveness measures based on heat removal-part 1. Definitions. Building and Environment, in press, doi:10.1016/j.buildenv.2006.03.016.] are applied to assess and compare two fundamental natural ventilation flows. We focus on the limiting cases of passive displacement and passive mixing ventilation flows during transient conditions. These transient flows occur when, for example, heat is purged from a building at night. Whilst it is widely recognised that mixing flows are less efficient at purging heat than displacement flows, our results indicate that, when a particular zone of a room is considered, displacement ventilation can result in lower effectiveness than mixing ventilation. When a room is considered as a whole, displacement ventilation yields higher effectiveness than mixing ventilation and we quantify these differences in terms of the geometry of the space and opening area. The proposed theoretical predictions are compared with effectiveness deduced from measurements made during laboratory experiments and show good agreement. © 2006 Elsevier Ltd. All rights reserved.

Ventilation effectiveness measures based on heat removal: Part 1. Definitions

The effectiveness of ventilation flows is considered from the perspective of buoyancy (or heat) removal from a space. This perspective is distinct from the standard in which the effectiveness is based on the concentrations of a neutrally buoyant contaminant/passive tracer. Three new measures of effectiveness are proposed based on the ability of a flow to flush buoyancy from a ventilated space. These measures provide estimates of instantaneous and time-averaged effectiveness for the entire space, and local effectiveness at any height of interest. From a generalisation of the latter, a vertical profile of effectiveness is defined. These measures enable quantitative comparisons to be made between different flows and they are applicable when there is a difference in density (as is typical due to temperature differences) between the interior environment and the replacement air. Applications, therefore, include natural ventilation, hybrid ventilation and a range of forced ventilation flows. Finally, we demonstrate how the ventilation effectiveness of a room may be assessed from simple traces of temperature versus time. © 2006 Elsevier Ltd. All rights reserved.

New ventilation efficiency measures based on buoyancy removal

New measures for estimating the efficiency of transient ventilation flows are proposed. These measures are developed by considering how effectively a ventilation system removes buoyancy from a space. This approach is distinct from standard efficiency measures which are, in general, based on the removal of a neutrally-buoyant passive tracer. Our new measures, based on (active) buoyancy removal, allow both the instantaneous and time-averaged efficiency of the entire space, or of any region within it, to be determined. In addition, expressions for determining vertical profiles of efficiency are proposed. These new measures enable the effectiveness of different flows to be compared directly and are applicable providing density (temperature) differences exist between the interior environment and the replacement air. Thus, they may be used to contrast the effectiveness of a broad range of building ventilation flows including natural, hybrid and forced ventilation.

The roles of energy and material efficiency in meeting steel industry CO2 targets.

Identifying strategies for reducing greenhouse gas emissions from steel production requires a comprehensive model of the sector but previous work has either failed to consider the whole supply chain or considered only a subset of possible abatement options. In this work, a global mass flow analysis is combined with process emissions intensities to allow forecasts of future steel sector emissions under all abatement options. Scenario analysis shows that global capacity for primary steel production is already near to a peak and that if sectoral emissions are to be reduced by 50% by 2050, the last required blast furnace will be built by 2020. Emissions reduction targets cannot be met by energy and emissions efficiency alone, but deploying material efficiency provides sufficient extra abatement potential.

Experimental investigation of dynamic response of acoustically forced turbulent premixed CH4/CO2/air flames

Increasing demand for energy and continuing increase in environmental as well as financial cost of use of fossil fuels drive the need for utilization of fuels from sustainable sources for power generation. Development of fuel-flexible combustion systems is vital in enabling the use of sustainable fuels. It is also important that these sustainable combustion systems meet the strict governmental emission legislations. Biogas is considered as one of the viable sustainable fuels that can be used to power modern gas turbines: However, the change in chemical, thermal and transport properties as well as change in Wobbe index due to the variation of the fuel constituents can have a significant effect on the performance of the combustor. It is known that the fuel properties have strong influence on the dynamic flame response; however there is a lack of detailed information regarding the effect of fuel compositions on the sensitivity of the flames subjected to flow perturbations. In this study, we describe an experimental effort investigating the response of premixed biogas-air turbulent flames with varying proportions of CH4 and CO2 to velocity perturbations. The flame was stabilized using a centrally placed conical bluff body. Acoustic perturbations were imposed to the flow using loud speakers. The flame dynamics and the local heat release rate of these acoustically excited biogas flames were studied using simultaneous measurements of OH and H2CO planar laser induced fluorescence. OH* chemiluminescence along with acoustic pressure measurements were also recorded to estimate the total flame heat release modulation and the velocity fluctuations. The measurements were carried out by keeping the theoretical laminar flame speed constant while varying the bulk velocity and the fuel composition. The results indicate that the flame sensitivity to perturbations increased with increased dilution of CH4 by CO2 at low amplitude forcing, while at high amplitude forcing conditions the magnitude of the flame response was independent of dilution.

Fast response CO2 sensor for automotive exhaust gas analysis

A fast response sensor for measuring carbon dioxide concentration has been developed for laboratory research and tested on a spark ignition engine. The sensor uses the well known infra-red absorption technique with a miniaturized detection system and short capillary sampling tubes, giving a time constant of approximately 5 milliseconds; this is sufficiently fast to observe changes in CO2 levels on a cycle-by-cycle basis under normal operating conditions. The sensor is easily located in the exhaust system and operates continuously. The sensor was tested on a standard production four cylinder spark-ignition engine to observe changes in CO2 concentration in exhaust gas under steady state and transient operating conditions. The processed sensor signal was compared to a standard air-to-fuel ratio (AFR) sensor in the exhaust stream and the results are presented here. The high frequency response CO2 measurements give new insights into both engine and catalyst transient operation. Copyright © 1999 Society of Automotive Engineers, Inc.

Flexible conversion ratio fast reactors: Overview

Conceptual designs of lead-cooled and liquid salt-cooled fast flexible conversion ratio reactors were developed. The performance achievable by the unity conversion ratio cores of these reactors was compared to an existing supercritical carbon dioxide-cooled (S-CO2) fast reactor design and an uprated version of an existing sodium-cooled fast reactor. All concepts have cores rated at 2400 MWt. The cores of the liquid-cooled reactors are placed in a large-pool-type vessel with dual-free level, which also contains four intermediate heat exchangers (IHXs) coupling a primary coolant to a compact and efficient supercritical CO2 Brayton cycle power conversion system. The S-CO2 reactor is directly coupled to the S-CO2 Brayton cycle power conversion system. Decay heat is removed passively using an enhanced reactor vessel auxiliary cooling system (RVACS) and a passive secondary auxiliary cooling system (PSACS). The selection of the water-cooled versus air-cooled heat sink for the PSACS as well as the analysis of the probability that the PSACS may fail to complete its mission was performed using risk-informed methodology. In addition to these features, all reactors were designed to be self-controllable. Further, the liquid-cooled reactors utilized common passive decay heat removal systems whereas the S-CO2 uses reliable battery powered blowers for post-LOCA decay heat removal to provide flow in well defined regimes and to accommodate inadvertent bypass flows. The multiple design limits and challenges which constrained the execution of the four fast reactor concepts are elaborated. These include principally neutronics and materials challenges. The neutronic challenges are the large positive coolant reactivity feedback, small fuel temperature coefficient, small effective delayed neutron fraction, large reactivity swing and the transition between different conversion ratio cores. The burnup, temperature and fluence constraints on fuels, cladding and vessel materials are elaborated for three categories of material - materials currently available, available on a relatively short time scale and available only with significant development effort. The selected fuels are the metallic U-TRU-Zr (10% Zr) for unity conversion ratio and TRU-Zr (75% Zr) for zero conversion ratio. The principal selected cladding and vessel materials are HT-9 and A533 or A508, respectively, for current availability, T-91 and 9Cr-1Mo steel for relatively short-term availability and oxide dispersion strengthened ferritic steel (ODS) available only with significant development. © 2009 Elsevier B.V. All rights reserved.

Removal of surface states and recovery of band-edge emission in InAs nanowires through surface passivation.

Surface states in semiconductor nanowires (NWs) are detrimental to the NW optical and electronic properties and to their light emission-based applications, due to the large surface-to-volume ratio of NWs and the congregation of defects states near surfaces. In this paper, we demonstrated an effective approach to eliminate surface states in InAs NWs of zinc-blende (ZB) and wurtzite (WZ) structures and a dramatic recovery of band edge emission through surface passivation with organic sulfide octadecylthiol (ODT). Microphotoluminescence (PL) measurements were carried out before and after passivation to study the dominant recombination mechanisms and surface state densities of the NWs. For WZ-NWs, we show that the passivation removed the surface states and recovered the band-edge emission, leading to a factor of ∼19 reduction of PL linewidth. For ZB-NWs, the deep surface states were removed and the PL peaks width became as narrow as ∼250 nm with some remaining emission of near band-edge surface states. The passivated NWs showed excellent stability in atmosphere, water, and heat environments. In particular, no observable changes occurred in the PL features from the passivated NWs exposed in air for more than five months.

Coagulation removal of melanoidins from biologically treated molasses wastewater using ferric chloride

The pigments (melanoidins) in molasses wastewater are refractory to conventional biological treatment. Ferric chloride was used as coagulant to remove color and chemical oxygen demand (COD) from molasses effluent. Using jar test procedure, main operating conditions such as pH and coagulant dosage were investigated. Under the optimum conditions, up to 86% and 96% of COD and color removal efficiencies were achieved. Residual turbidity in supernatant was less than 5 NTU and Fe3+ concentration was negligible because of effective destabilization and subsequent sedimentation. The results of high performance size exclusion chromatography (HPSEC) show that low molecular weight (MW) fraction of melanoidins is more reactive than high MW fraction and increase in the concentration of the lowest MW organic group is related to the capacity of charge neutralization. Aggregate size measurement reveals the size effect on the settleability of flocs formed, with larger flocs settling more rapidly. Charge neutralization and co-precipitation are proposed as predominant coagulation mechanism under the optimum conditions. (C) 2009 Elsevier B.V. All rights reserved.