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.

An investigation of the kinetics of CO 2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO 2 at temperatures of ca. 750°C of a synthetic sorbent composed of 15wt% mayenite (Ca 12Al 14O 33) 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. © 2011 Elsevier Ltd.

CFD modeling of single-phase flow in a packed bed with MRI validation

Computational fluid dynamics (CFD) simulations are becoming increasingly widespread with the advent of more powerful computers and more sophisticated software. The aim of these developments is to facilitate more accurate reactor design and optimization methods compared to traditional lumped-parameter models. However, in order for CFD to be a trusted method, it must be validated using experimental data acquired at sufficiently high spatial resolution. This article validates an in-house CFD code by comparison with flow-field data obtained using magnetic resonance imaging (MRI) for a packed bed with a particle-to-column diameter ratio of 2. Flows characterized by inlet Reynolds numbers, based on particle diameter, of 27, 55, 111, and 216 are considered. The code used employs preconditioning to directly solve for pressure in low-velocity flow regimes. Excellent agreement was found between the MRI and CFD data with relative error between the experimentally determined and numerically predicted flow-fields being in the range of 3-9%. © 2012 American Institute of Chemical Engineers (AIChE).

Bending of nanoscale filament assemblies by elastocapillary densification

We report a mechanism by which nanoscale filaments self-assemble into asymmetric aggregates by elastocapillary action. Specifically, capillary rise of liquid into an asymmetric pattern of vertically aligned filaments causes the filaments to deflect laterally during elastocapillary densification. We quantitatively show that the lateral deflection can be controlled precisely by the pattern shape and the coupling strength among the filaments. We exploit this mechanism to fabricate asymmetric micropillars and multidirectional bridges of densely packed carbon nanotubes. Analogous behavior occurs as biological filaments interact with liquids, and these findings enable scalable fabrication of anisotropic filament assemblies for manipulating surface interactions between solids and liquids. © 2010 The American Physical Society.

Novel ZnO nanorod films by chemical solution deposition for planar device applications.

Smooth and continuous ZnO films consisting of densely packed ZnO nanorods (NRs), which can be used for electronic device fabrication, were synthesized using a hydro-thermo-chemical solution deposition method. Such devices would have the novelty of high performance, benefiting from the inherited unique properties of the nanomaterials, and can be fabricated on these smooth films using a conventional, low cost planar process. Photoluminescence measurements showed that the NR films have much stronger shallow donor to valence band emissions than those from discrete ZnO NRs, and hence have the potential for the development of ZnO light emission diodes and lasers, etc. The NR films have been used to fabricate large area surface acoustic wave devices by conventional photolithography. These demonstrated two well-defined resonant peaks and their potential for large area device applications. The chemical solution deposition method is simple, reproducible, scalable and economic. These NR films are suitable for large scale production on cost-effective substrates and are promising for various fields such as sensing systems, renewable energy and optoelectronic applications.

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.

Reversible CO2 absorption by the 6H perovskite Ba 4Sb2O9

A novel compound for carbon capture and storage (CCS) applications, the 6H perovskite Ba4Sb2O9, was found to be able to absorb CO2 through a chemical reaction at 873 K to form barium carbonate and BaSb2O6. This absorption was shown to be reversible through the regeneration of the original Ba4Sb 2O9 material upon heating above 1223 K accompanied by the release of CO2. A combined synchrotron X-ray diffraction, thermogravimetric, and microscopy study was carried out to characterize first the physical absorption properties and then to analyze the structural evolution and formation of phases in situ. Importantly, through subsequent carbonation and regeneration of the material over 100 times, it was shown that the combined absorption and regeneration reactions proceed without any significant reduction in the CO2 absorption capacity of the material. After 100 cycles the capacity of Ba4Sb2O9 was ∼0.1 g (CO 2)/g (sorbent), representing 73% of the total molar capacity. This is the first report of a perovskite-type material showing such good properties, opening the way for studies of new classes of inorganic oxide materials with stable and flexible chemical compositions and structures for applications in carbon capture. © 2013 American Chemical Society.