In situ studies of materials for high temperature CO2 capture and storage.

Carbon capture and storage (CCS) offers a possible solution to curb the CO2 emissions from stationary sources in the coming decades, considering the delays in shifting energy generation to carbon neutral sources such as wind, solar and biomass. The most mature technology for post-combustion capture uses a liquid sorbent, amine scrubbing. However, with the existing technology, a large amount of heat is required for the regeneration of the liquid sorbent, which introduces a substantial energy penalty. The use of alternative sorbents for CO2 capture, such as the CaO-CaCO3 system, has been investigated extensively in recent years. However there are significant problems associated with the use of CaO based sorbents, the most challenging one being the deactivation of the sorbent material. When sorbents such as natural limestone are used, the capture capacity of the solid sorbent can fall by as much as 90 mol% after the first 20 carbonation-regeneration cycles. In this study a variety of techniques were employed to understand better the cause of this deterioration from both a structural and morphological standpoint. X-ray and neutron PDF studies were employed to understand better the local surface and interfacial structures formed upon reaction, finding that after carbonation the surface roughness is decreased for CaO. In situ synchrotron X-ray diffraction studies showed that carbonation with added steam leads to a faster and more complete conversion of CaO than under conditions without steam, as evidenced by the phases seen at different depths within the sample. Finally, in situ X-ray tomography experiments were employed to track the morphological changes in the sorbents during carbonation, observing directly the reduction in porosity and increase in tortuosity of the pore network over multiple calcination reactions

Development and performance of iron based oxygen carriers containing calcium ferrites for chemical looping combustion and production of hydrogen

Chemical looping combustion (CLC) is a cyclic process in which an oxygen carrier (OC), is firstly reduced by a fuel, e.g. syngas, and then oxidised in air to produce heat. If the OC is Fe2O3, the oxidation can take place in steam to produce hydrogen, i.e. chemical looping hydrogen production (CLH). This paper presents an investigation of CaO modified Fe2O3 OCs for CLC and CLH. The performance of the mechanically mixed OCs were examined in a thermogravimetric analyser and a fluidised bed. It was found that the addition of CaO gives cyclic stability and additional capacity to produce hydrogen via CLH, at the expense of reduced oxygen carrying capacity for CLC, owing to the formation of calcium ferrites, such as Ca2Fe2O5.The authors would like to thank Prof. Clare Grey for her invaluable help in the XRD analysis and Z. Saracevic for support in operating the gas adsorption analyser. This work was supported by the Engineering and Physical Sciences Research Council (EPSRC grant EP/I070912/1). The first author is grateful to IDB (Islamic Development Bank) - Cambridge International Scholarship body for financial support for PhD study. W. L acknowledges funding from the National Research Foundation (NRF), Prime Minister’s Office, Singapore under its Campus for Research Excellence and Technological Enterprise (CREATE) programme.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.ijhydene.2015.11.06

Sensitivity of chemical-looping combustion to particle reaction kinetics

A simple simulation for chemical-looping combustion (CLC) is discussed: two, coupled fluidised reactors with steady circulation of particles of oxygen carrier between them. In particular, the sensitivity of CLC to different particle kinetics is investigated. The results show that the system is relatively insensitive to different kinetics when the mean residence time of particles in each reactor is greater than the time taken for them to react completely.This is the final published version. It first appeared at http://www.sciencedirect.com/science/article/pii/S0009250916302779

Modelling rates of gasification of a char particle in chemical looping combustion

Rates of gasification of lignite char were compared when gasification with CO2 was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. An analytical solution assuming pseudo-binary diffusion of species 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 results are compared with a full numerical model using the Stefan-Maxwell equations. Excellent agreement was observed between the rates predicted by the two models and those observed experimentally at T ≤ 1123 K. At 1173 K, the pseudo-binary model predicted slightly higher rates than the full numerical solution. It was found that a significant share of the error of the predicted rates with the analytical solution was caused by an underestimation of intraparticle diffusional resistance rather than by assuming a pseudo-binary system external to the particle. Both models suggested that 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 ~20% conversion when (i) the surface area for reaction was a maximum and (ii) because of the accompanying increase in porosity, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle.EPSRCThis is the author accepted manuscript. The final version is now available at http://www.sciencedirect.com/science/article/pii/S1540748914003150

Limitations on Fluid Grid Sizing for Using Volume-Averaged Fluid Equations in Discrete Element Models of Fluidized Beds

Bubbling and slugging fluidization were simulated in 3D cylindrical fluidized beds using a discrete element model with computational fluid dynamics (DEM-CFD). A CFD grid was used in which the volume of all fluid cells was equal. Ninety simulations were conducted with different fluid grid cell lengths in the vertical (dz) and radial (dr) directions to determine at what fluid grid sizes, as compared to the particle diameter (dp), the volume-averaged fluid equations broke down and the predictions became physically unrealistic. Simulations were compared with experimental results for time-averaged particle velocities as well as frequencies of pressure oscillations and bubble eruptions. The theoretical predictions matched experimental results most accurately when dz = 3-4 dp, with physically unrealistic predictions produced from grids with lower dz. Within the valid range of dz, variations of dr did not have a significant effect on the results.CMB acknowledges the Gates Cambridge Trust for funding his research.This is the author accepted manuscript. The final version is available from ACS via http://dx.doi.org/10.1021/acs.iecr.5b0318

Improving hydrogen yields, and hydrogen: Steam ratio in the chemical looping production of hydrogen using Ca<inf>2</inf>Fe<inf>2</inf>O<inf>5</inf>

A thermodynamic property of Ca2Fe2O5 was exploited to improve the efficiency of the steam-iron process to produce hydrogen. The ability of reduced Ca2Fe2O5 to convert a higher fraction of steam to hydrogen than chemically unmodified Fe was demonstrated in a packed bed. At 1123 K, the use of Ca2Fe2O5 achieved an equilibrium conversion of steam to hydrogen of 75%, in agreement with predicted thermodynamics and substantially higher than that theoretically achievable by iron oxide, viz. 62%. Furthermore, in Ca2Fe2O5, the full oxidation from Fe(0) to Fe(III) can be utilised for hydrogen production – an improvement from the Fe to Fe3O4 transition for unmodified iron. Thermodynamic considerations demonstrated in this study allow for the rational design of oxygen carriers in the future. Modifications of reactors to capitalise on this new material are discussed.Dr Matthew T. Dunstan is acknowledged for help with the XRD analysis. M.S.C.C acknowledges financial support from an EPSRC Doctoral Training Grant. W.L and Y.Y acknowledge funding from the National Research Foundation (NRF), Prime Minister’s Office, Singapore under its Campus for Research Excellence and Technological Enterprise (CREATE) programme.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.cej.2016.03.13

The incidence and clinical burden of respiratory syncytial virus disease identified through hospital outpatient presentations in Kenyan children

There is little information that describe the burden of respiratory syncytial virus (RSV) associated disease in the tropical African outpatient setting. Methods We studied a systematic sample of children aged <5 years presenting to a rural district hospital in Kenya with acute respiratory infection (ARI) between May 2002 and April 2004. We collected clinical data and screened nasal wash samples for RSV antigen by immunofluorescence. We used a linked demographic surveillance system to estimate disease incidence. Results Among 2143 children tested, 166 (8%) were RSV positive (6% among children with upper respiratory tract infection and 12% among children with lower respiratory tract infection (LRTI). RSV was more likely in LRTI than URTI (p<0.001). 51% of RSV cases were aged 1 year or over. RSV cases represented 3.4% of hospital outpatient presentations. Relative to RSV negative cases, RSV positive cases were more likely to have crackles (RR = 1.63; 95% CI 1.34–1.97), nasal flaring (RR = 2.66; 95% CI 1.40–5.04), in-drawing (RR = 2.24; 95% CI 1.47–3.40), fast breathing for age (RR = 1.34; 95% CI 1.03–1.75) and fever (RR = 1.54; 95% CI 1.33–1.80). The estimated incidence of RSV-ARI and RSV-LRTI, per 100,000 child years, among those aged <5 years was 767 and 283, respectively. Conclusion The burden of childhood RSV-associated URTI and LRTI presenting to outpatients in this setting is considerable. The clinical features of cases associated with an RSV infection were more severe than cases without an RSV diagnosis

Use of a Chemical-Looping Reaction to Determine the Residence Time Distribution of Solids in a Circulating Fluidized Bed

The residence time distribution (RTD) of solids in various sections of a circulating fluidized bed (CFB) is of great importance for design and operation but is often difficult to determine experimentally. A noninvasive method is described, for which the RTD was derived from temporal measurements of the temperature following the initiation of a chemical-looping reaction. To demonstrate the method, a CuO-based oxygen carrier was used in a small-scale CFB, and measurements were made in the fuel reactor, operated as a bubbling fluidized bed. The measurements were fitted to the tanks-in-series model, modified to account for heat losses from the reactor. There was excellent agreement between the model and the experiment. Limitations and further improvements of the method are discussed, also with respect to larger reactors.This work is supported by the Engineering and Physical Sciences Research Council (EPSRC Grant EP/I010912/1).This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/ente.20160014

Chemical looping epoxidation

Chemical looping epoxidation of ethylene was demonstrated, whereby the sole oxidant was a solid oxygen carrier, 15 wt% Ag supported on SrFeO3. Ethylene reacted with a bed of carrier particles, without any O2(g) in the feed, to produce ethylene oxide (EO) and CO2. Following the reduction by the C2H4 of the SrFeO3, it was regenerated by passing air through the bed. The rate of reoxidation was slow, with full regeneration being achieved only by prolonged oxidation at elevated temperatures. A striking synergy between Ag and SrFeO3 was observed solely when they were in intimate contact, suggesting a basis for a proposed reaction mechanism

Significance of gasification during oxy-fuel combustion of a lignite char in a fluidised bed using a fast UEGO sensor

In oxy-fuel combustion, fuel is combusted in a mixture of O₂ and recycled flue gas, i.e. the N₂ is replaced by CO₂ with the O₂ supplied from an air separation unit. The resulting gas consists largely of steam and CO2, which would be ready for sequestration when dried. In this work, the rate of reaction of particles of lignite char, typically 1200 μm diameter, in a fluidised bed reactor was determined using mixtures of O₂ with either CO₂ (“oxy-fuel”) or N₂. A universal exhaust-gas oxygen (UEGO) sensor enabled rapid measurements of the oxygen partial pressures in the off-gas, representing a novel application of this type of sensor. It was found that the rate of combustion of the particles in oxy-fuel is much more sensitive to temperature than in the equivalent O₂ and N₂ mixture. This is because for bed temperatures >∼1000 K particle combustion in mixtures of N₂ and O₂ is rate controlled by external mass transfer, which does not increase significantly with temperature. In contrast, using oxy-fuel, as the temperature increases, gasification by the high concentrations of CO₂ present becomes increasingly significant. At low temperatures, e.g. ∼1000 K, rates of combustion in oxy-fuel were lower than those in mixtures of O₂ and N₂ containing the same mole fraction of O₂ owing, primarily, to the lower diffusivities of O2 in CO₂ compared to O₂ in N₂ under conditions at which external mass transfer is still a significant factor in controlling the rate of reaction. At higher temperatures, e.g. 1223 K, oxy-fuel combustion rates were significantly higher than those in O₂ and N₂. The point at which oxy-fuel combustion becomes more rapid than in mixtures of O₂ and N₂ depends not only on temperature but also on the ratio of O₂ to CO₂ or N₂, respectively. A numerical model was developed to account for external mass transfer, changes in the temperature of the particle and for the effect of gasification under oxy-fuel conditions. The model confirmed that, at high temperatures, the high concentration of CO₂ at the surface of the burning particle in the oxy-fuel mixture led to an increase in the overall rate of carbon conversion via CO₂ + C → 2CO, whilst the rate of reaction with O₂ was limited by mass transfer. Good agreement was observed between the rates predicted by the numerical model and those observed experimentally.Financial support from the Engineering and Physical Sciences Research Council (Grant reference number: EP/G063265/1) and the Consejo Nacional de Ciencia y Tecnología (CONACYT) is also acknowledged.This is the author accepted manuscript. The final version is available from Elsevier via http://dx.doi.org/10.1016/j.fuel.2014.10.02