Effect of Steam Injection during Carbonation on the Multicyclic Performance of Limestone (CaCO3) under Different Calcium Looping Conditions: A Comparative Study.

This study explores the effect of steam addition during carbonation on the multicyclic performance of limestone under calcium looping conditions compatible with (i) CO2 capture from postcombustion gases (CCS) and with (ii) thermochemical energy storage (TCES). Steam injection has been proposed to improve the CO2 uptake capacity of CaO-based sorbents when the calcination and carbonation loops are carried out in CCS conditions: at moderate carbonation temperatures (∼650 °C) under low CO2 concentration (typically ∼15% at atmospheric pressure). However, the recent proposal of calcium-looping as a TCES system for integration into concentrated solar power (CSP) plants has aroused interest in higher carbonation temperatures (∼800-850 °C) in pure CO2. Here, we show that steam benefits the multicyclic behavior in the milder conditions required for CCS. However, at the more aggressive conditions required in TCES, steam essentially has a neutral net effect as the CO2 uptake promoted by the reduced CO2 partial pressure but also is offset by the substantial steam-promoted mineralization in the high temperature range. Finally, we also demonstrate that the carbonation rate depends exclusively on the partial pressure of CO2, regardless of the diluting gas employed.

Correction: Limestone calcination under calcium-looping conditions for CO2 capture and thermochemical energy storage in the presence of H2O: an in situ XRD analysis.

Correction for 'Limestone calcination under calcium-looping conditions for CO2 capture and thermochemical energy storage in the presence of H2O: an in situ XRD analysis' by Jose Manuel Valverde et al., Phys. Chem. Chem. Phys., 2017, 19, 7587-7596.

Limestone calcination under calcium-looping conditions for CO2 capture and thermochemical energy storage in the presence of H2O: an in situ XRD analysis.

This work reports an in situ XRD analysis of whether the calcination/carbonation behavior of natural limestone (CaCO3) is affected by the addition of H2O to the calciner at a very low concentration under relevant Calcium-Looping (CaL) conditions for CO2 capture in coal fired power plants (CFPP) and Thermochemical Energy Storage (TCES) in Concentrated Solar Power plants (CSP). Previous studies have demonstrated that the presence of steam in the calciner at a high concentration yields a significant increase in the reaction rate. However, a further undesired consequence is the serious deterioration of the CaO mechanical strength, which would lead to particle attrition and mass loss in any CaL process based on the use of circulating fluidized beds. The results presented in this manuscript on the time evolution of the wt% and crystallite size of the phases involved in the calcination/carbonation reactions indicate that the calcination rate is still notably increased by the presence of H2O at very low concentrations whereas the reactivity toward carbonation and crystal structure of the formed CaO are not essentially affected, which suggests that the CaO mechanical strength is not impaired. Thus, the benefit of using steam for calcination in the CaL process could be still retained while at the same time particle attrition would not be promoted.

Effect of dolomite decomposition under CO2 on its multicycle CO2 capture behaviour under calcium looping conditions.

One of the major drawbacks that hinder the industrial competitiveness of the calcium looping (CaL) process for CO2 capture is the high temperature (∼930-950 °C) needed in practice to attain full calcination of limestone in a high CO2 partial pressure environment for short residence times as required. In this work, the multicycle CO2 capture performance of dolomite and limestone is analysed under realistic CaL conditions and using a reduced calcination temperature of 900 °C, which would serve to mitigate the energy penalty caused by integration of the CaL process into fossil fuel fired power plants. The results show that the fundamental mechanism of dolomite decomposition under CO2 has a major influence on its superior performance compared to limestone. The inert MgO grains resulting from dolomite decomposition help preserve a nanocrystalline CaO structure wherein carbonation in the solid-state diffusion controlled phase is promoted. The major role played by the dolomite decomposition mechanism under CO2 is clearly demonstrated by the multicycle CaO conversion behaviour observed for samples decomposed at different preheating rates. Limestone decomposition at slow heating rates yields a highly crystalline and poorly reactive CaCO3 structure that requires long periods to fully decarbonate and shows a severely reduced capture capacity in subsequent cycles. On the other hand, the nascent CaCO3 produced after dolomite half-decomposition consists of nanosized crystals with a fast decarbonation kinetics regardless of the preheating rate, thus fully decomposing from the very first cycle at a reduced calcination temperature into a CaO skeleton with enhanced reactivity as compared to limestone derived CaO.

Thermal decomposition of dolomite under CO2: insights from TGA and in situ XRD analysis.

Thermal decomposition of dolomite in the presence of CO2 in a calcination environment is investigated by means of in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The in situ XRD results suggest that dolomite decomposes directly at a temperature around 700 °C into MgO and CaO. Immediate carbonation of nascent CaO crystals leads to the formation of calcite as an intermediate product of decomposition. Subsequently, decarbonation of this poorly crystalline calcite occurs when the reaction is thermodynamically favorable and sufficiently fast at a temperature depending on the CO2 partial pressure in the calcination atmosphere. Decarbonation of this dolomitic calcite occurs at a lower temperature than limestone decarbonation due to the relatively low crystallinity of the former. Full decomposition of dolomite leads also to a relatively low crystalline CaO, which exhibits a high reactivity as compared to limestone derived CaO. Under CO2 capture conditions in the Calcium-Looping (CaL) process, MgO grains remain inert yet favor the carbonation reactivity of dolomitic CaO especially in the solid-state diffusion controlled phase. The fundamental mechanism that drives the crystallographic transformation of dolomite in the presence of CO2 is thus responsible for its fast calcination kinetics and the high carbonation reactivity of dolomitic CaO, which makes natural dolomite a potentially advantageous alternative to limestone for CO2 capture in the CaL technology as well as SO2in situ removal in oxy-combustion fluidized bed reactors.

Crystallographic transformation of limestone during calcination under CO2.

The calcination reaction of limestone (CaCO3) to yield lime (CaO) is at the heart of many industrial applications as well as natural processes. In the recently emerged calcium-looping technology, CO2 capture is accomplished by the carbonation of CaO in a gas-solid reactor (carbonator). CaO is derived by the calcination of limestone in a calciner reactor under necessarily high CO2 partial pressure and high temperature. In situ X-ray diffraction (XRD) has been employed in this work to gain further insight into the crystallographic transformation that takes place during the calcination of limestone under CO2, at partial pressures (P) close to the equilibrium pressure (Peq) and at high temperature. Calcination under these conditions becomes extremely slow. The in situ XRD analysis presented here suggests the presence of an intermediate metastable CaO* phase stemming from the parent CaCO3 structure. According to the reaction mechanism proposed elsewhere, the exothermicity of the CaO* → CaO transformation and high values of P/Peq inhibit the nucleation of CaO at high temperatures. The wt% of CaO* remains at a relatively high level during slow calcination. Two diverse stages have been identified in the evolution of CaO crystallite size, L. Initially, L increases with CaCO3 conversion, following a logarithmic law. Slow calcination allows the crystallite size to grow up from a few nanometers at nucleation up to around 100 nm near the end of conversion. Otherwise, quick calcination at relatively lower CO2 concentrations limits CaO crystallite growth. Once calcination reaches an advanced state, the presence of CaO* drops to zero and the rate of increase of the CaO crystallite size is significantly hindered. Arguably, the first stage in CaO crystallite growth is driven by aggregation of the metastable CaO* nanocrystals, due to surface attractive forces, whereas the second one is consistent with sintering of the aggregated CaO crystals, and persists with time after full calcination is attained. Our analysis shows that the main mechanism responsible for the increase of CaO crystallite size (and thus for undermining the reactivity of the CaO) under high CO2 partial pressure is enhanced aggregation, whereas CaO sintering is relatively less relevant, as would be expected for calcination temperatures well below the Tamman temperature.

Convection and fluidization in oscillatory granular flows: The role of acoustic streaming.

Convection and fluidization phenomena in vibrated granular beds have attracted a strong interest from the physics community since the last decade of the past century. As early reported by Faraday, the convective flow of large inertia particles in vibrated beds exhibits enigmatic features such as frictional weakening and the unexpected influence of the interstitial gas. At sufficiently intense vibration intensities surface patterns appear bearing a stunning resemblance with the surface ripples (Faraday waves) observed for low-viscosity liquids, which suggests that the granular bed transits into a liquid-like fluidization regime despite the large inertia of the particles. In his 1831 seminal paper, Faraday described also the development of circulation air currents in the vicinity of vibrating plates. This phenomenon (acoustic streaming) is well known in acoustics and hydrodynamics and occurs whenever energy is dissipated by viscous losses at any oscillating boundary. The main argument of the present paper is that acoustic streaming might develop on the surface of the large inertia particles in the vibrated granular bed. As a consequence, the drag force on the particles subjected to an oscillatory viscous flow is notably enhanced. Thus, acoustic streaming could play an important role in enhancing convection and fluidization of vibrated granular beds, which has been overlooked in previous studies. The same mechanism might be relevant to geological events such as fluidization of landslides and soil liquefaction by earthquakes and sound waves.

Fluidization of nanopowders: a review.

Nanoparticles (NPs) are applied in a wide range of processes, and their use continues to increase. Fluidization is one of the best techniques available to disperse and process NPs. NPs cannot be fluidized individually; they fluidize as very porous agglomerates. The objective of this article is to review the developments in nanopowder fluidization. Often, it is needed to apply an assistance method, such as vibration or microjets, to obtain proper fluidization. These methods can greatly improve the fluidization characteristics, strongly increase the bed expansion, and lead to a better mixing of the bed material. Several approaches have been applied to model the behavior of fluidized nanopowders. The average size of fluidized NP agglomerates can be estimated using a force balance or by a modified Richardson and Zaki equation. Some first attempts have been made to apply computational fluid dynamics. Fluidization can also be used to provide individual NPs with a thin coating of another material and to mix two different species of nanopowder. The application of nanopowder fluidization in practice is still limited, but a wide range of potential applications is foreseen. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s11051-012-0737-4) contains supplementary material, which is available to authorized users.

Guía de intervención grupal para el abordaje del tabaquismo en Atención Primaria

Contiene: introducción, objetivo y población diana, intervención grupal para el abordaje del tabaquismo, guión de sesiones, aspectos organizativos, recomendaciones finales y evaluación.

Types of gas fluidization of cohesive granular materials.

Some years ago it was shown that gas-fluidized powders may transit from solid-like to fluid-like fluidization prior to bubbling, shedding light on a long-standing controversy on the nature of "homogeneous" fluidization. In this paper it is shown that some gas-fluidized powders may also transit from the fluid-like regime to elutriation, with full suppression of the bubbling regime. We provide a diagram that can be used to predict these types of fluidization exhibited by cohesive powders based on simple phenomenological equations in which particle aggregation due to attractive forces is a key ingredient.

High viscosity gas fluidization of fine particles: An extended window of quasihomogeneous flow.

We explore the role of gas viscosity in the behavior of gas-fluidized beds of fine powders by means of experimental measurements using nitrogen and neon as fluidizing gases, and theoretical considerations. The existence of a nonbubbling fluidlike regime has been recently observed in beds of fine powders fluidized with nitrogen. Our experiments with neon reveal a discontinuous transition from heterogeneous fluidization to a highly expanded homogeneous fluidization state. We point out that increasing gas viscosity enhances the coherence of agglomerate swarms, which promotes a local void-splitting mechanism, thus improving the uniformity of fluidization. Our theoretical analysis predicts that further increase of gas viscosity would produce a full suppression of the bubbling regime, i.e., the uniformly fluidized bed would undergo a direct transition to a turbulent regime as seen in beds of nanoparticles fluidized by nitrogen and in liquid-fluidized beds of moderate-density beads.

Effect of compaction history on the fluidization behavior of fine cohesive powders.

Fine particles agglomerate in the fluidized state due to the strength of interparticle attractive forces as compared to particle weight. Interparticle adhesion can be largely increased by consolidation stresses applied during powder handling. As a consequence, fragments of the consolidated powder may persist when the powder is fluidized, which gives rise to large agglomerates of strongly adhered particles in fluidization. This history-dependent effect can be minimized by coating the particles with surface additives such as silica nanoparticles. In this paper, we investigate the effect of high consolidation stresses sigma(c) previously applied to samples of silica-coated fine particles on their fluidization behavior. Our experimental measurements show that, even though homogeneous fluidization is still observed, the average agglomerate size and fractal dimension of the agglomerates increase as sigma(c) is increased. Bed expansion in the fluidized state is hindered by previously applied high consolidations, which we attribute to an increase of the largest stable size of mesoscopic fluid pockets. As a consequence, we observe that the initiation of macroscopic bubbling is delayed up to larger values of the fluid velocity.

Adaptación a los cambios, evaluación del desempeño y relación con incentivos de los recursos humanos en el sector salud de Costa Rica: estado del arte / Adapting to changes, performance evaluation and relation with human resources incentives in Costa Rica's health sector: state of the art

Se expone, de manera esquemática, una síntesis de la información y el conocimiento disponible a partir de fuentes primarias y secundarias consultadas, en relación con áreas priorizadas en el campo de recursos humanos a partir del trabajo realizado por un grupo ad hoc. Las áreas críticas priorizadas fueron : a) adaptación a los cambios en las funciones institucionales y/o modelo de prestación de servicios, b) evaluación del desempeño y relación con incentivos y c) política de capacitación