NiO/CaAl2O4 as active oxygen carrier for low temperature chemical looping applications

The implementation of CO2 capture systems in conventional processes has been proposed by the IPCC as an effective way to reduce anthropogenic CO2 emissions. However, these capture systems may represent an important decrease in the global efficiency for conventional processes. Chemical Looping has already been demonstrated as a promising technology for more efficient CO2 capture. Novel reactor concepts have been proposed in the literature, in which the reactions take place at lower temperatures with increased overall energy efficiency. However, few investigations have been carried out regarding the behaviour of oxygen carriers at relatively low operating temperatures. In this work, an active Ni-based oxygen carrier supported on CaAl2O4 inert material has been tested and characterized. The oxygen carrier has shown a promising behaviour for low temperature applications. However, it has been demonstrated that the oxygen carrier has to be pre-treated because of an interesting activation process which takes place only at high reduction temperatures. Oxygen carrier activation is caused by a reorganization of superficial nickel. Fresh oxygen carrier is covered by a layer of nickel with a strong interaction with the support. However, once the sample is reduced at high temperatures Ni is reorganized into small grains with reduced interaction with the support. This results in an enhancement in the reactivity and a higher oxygen transport capacity. After about 200 redox cycles, a small decrease in the solid conversion is observed due to agglomeration of the NiO grains. Nevertheless, the redox kinetics is still sufficiently fast for low temperature applications, provided that the oxygen carrier is pre-activated. The kinetics rates for the gas–solid reactions and gas-phase catalytic reactions have been determined, which can be used to predict the performance of the activated NiO/CaAl2O4 oxygen carrier for low temperature chemical looping applications

On the internal solids circulation rates in freely-bubbling gas-solid fluidized beds

The solids mass flux distribution and internal solids circulation rates in freely-bubbling gas-solid fluidized beds has been studied in detail in a pseudo-2D column. A non-invasive Particle Image Velocimetry (PIV) combined with Digital Image Analysis (DIA) technique has been further extended to investigate and quantify the gas and solids phase properties simultaneously for different particle types and sizes (all Geldart B type) at different fluidization velocities. It is found that the solids fluxes increase strongly, practically linearly, as a function of the vertical position and depend on the excess gas velocity but not on the particle size, while the most often used phenomenological two-phase fluidized bed models assume the vertical solids fluxes to be constant. To further investigate this important discrepancy, the underlying assumptions of the phenomenological models have been validated, especially concerning the average solids fraction inside the bubbles, the laterally and time-averaged axial bubble fraction profile (or visual bubble flow rate) and the wake parameter (the amount of solids carried along a bubble relative to the bubble volume). To this end, the PIV/DIA technique was further extended and a new method for the determination of the wake parameter is proposed. From the experimental results, it was concluded that i) the average solids fraction inside the bubbles is about 2.5–3% for glass beads and alumina particles and is practically independent of the excess gas velocity and particle size; ii) the measured laterally and time-averaged bubble fractions are considerably lower compared to often used correlations from literature, which would lead to a significant over-prediction of the visual bubble flow rate and iii) the wake parameter depends strongly on the bubble size and with the developed correlation the axial solids mass fluxes as a function of the vertical position can be well described. Finally, the influence of these findings was evaluated by performing a sensitivity analysis with an existing phenomenological model for fluidized beds with the new values and closures considering the case of the heterogeneously catalyzed steam methane reforming. With the developed findings and correlations the predictions with the two-phase phenomenological models can be further improved, especially concerning the hydrodynamics of the solids phase

NiO/CaAl2O4 as active oxygen carrier for low temperature chemical looping applications

The implementation of CO2 capture systems in conventional processes has been proposed by the IPCC as an effective way to reduce anthropogenic CO2 emissions. However, these capture systems may represent an important decrease in the global efficiency for conventional processes. Chemical Looping has already been demonstrated as a promising technology for more efficient CO2 capture. Novel reactor concepts have been proposed in the literature, in which the reactions take place at lower temperatures with increased overall energy efficiency. However, few investigations have been carried out regarding the behaviour of oxygen carriers at relatively low operating temperatures. In this work, an active Ni-based oxygen carrier supported on CaAl2O4 inert material has been tested and characterized. The oxygen carrier has shown a promising behaviour for low temperature applications. However, it has been demonstrated that the oxygen carrier has to be pre-treated because of an interesting activation process which takes place only at high reduction temperatures. Oxygen carrier activation is caused by a reorganization of superficial nickel. Fresh oxygen carrier is covered by a layer of nickel with a strong interaction with the support. However, once the sample is reduced at high temperatures Ni is reorganized into small grains with reduced interaction with the support. This results in an enhancement in the reactivity and a higher oxygen transport capacity. After about 200 redox cycles, a small decrease in the solid conversion is observed due to agglomeration of the NiO grains. Nevertheless, the redox kinetics is still sufficiently fast for low temperature applications, provided that the oxygen carrier is pre-activated. The kinetics rates for the gas–solid reactions and gas-phase catalytic reactions have been determined, which can be used to predict the performance of the activated NiO/CaAl2O4 oxygen carrier for low temperature chemical looping applications

Determination of the bubble-to-emulsion phase mass transfer coefficient in gas-solid fluidized beds using a non-invasive infra-red technique

The theoretical approach for the bubble-to-emulsion phase mass exchange in bubbling gas-solid fluidized beds developed by Davidson and Harrison in the early 60’s is still widely applied in phenomenological models, mainly because of lack of more detailed experimental data to improve the description. In this study a novel infrared transmission technique that allows the direct and non-invasive measurement of gas concentration profiles inside bubbles with a high temporal resolution has been used for the validation of the theoretical description for the gas exchange. At first, the experimental technique has been further improved concerning the selective removal of particles raining through the bubbles, as well as the reconstruction of tracer gas concentration profiles throughout the gas bubble. The bubble-to-emulsion phase mass transfer coefficients have been measured by injecting tracer gas bubbles into incipiently fluidized beds and beds at freely-bubbling conditions, for beds consisting of glass beads of different particle size and with different injected bubble diameters. The results show that the Davidson and Harrison approach can reasonably well describe the mass exchange for isolated bubbles injected into a bed at minimum fluidization conditions. However, experiments carried out in a freely bubbling bed have shown that the mass exchange rate is considerably enhanced due to the increased gas through-flow through the bubbles. An empirical correlation (with deviations within only 20%) for the volumetric bubble-to-emulsion phase mass transfer coefficient has been developed based on the bubble size and superficial gas velocity, where it is noted that in this work the convective contribution in the mass exchange is dominant

Pd-based metallic supported membranes : high temperature stability and fluidized bed reactor testing

The present work focuses on the study of a metallic supported Pd–Ag membrane for high temperature applications with a particular attention to long-term stability. In this work, a metallic supported thin-film Pd–Ag membrane has been tested for more than 800 h and sustained hydrogen perm-selectivities higher than 200000 have been measured. Furthermore, it has been demonstrated that there is no interaction of the membrane with the Ni/CaAl2O4 reforming catalyst particles, thus resulting in a constant permeance in the fluidized bed membrane reactor mode. The membrane has been tested under steam and autothermal reforming of methane conditions and the membrane performance has been quantified in terms of the hydrogen recovery and separation factors demonstrating a good reactor performance accomplishing an enhancement in the process efficiency by in-situ selective H2 separation. A decrease in ideal perm-selectivity has been observed at high temperatures (600 °C). Small defects at the Pd/Ag surface as a result of interaction of the Pd/Ag later with the metallic support have been observed in after test membrane characterization, which provides appreciated information for the improvement in the performance and production of future membranes