Ca-looping for postcombustion CO2 capture: A comparative analysis on the performances of dolomite and limestone

The low cost and wide availability of natural limestone (CaCO3) is at the basis of the industrial competitiveness of the Ca-looping (CaL) technology for postcombustion CO2 capture as already demonstrated by ~1Mwt scale pilot projects. A major focus of studies oriented towards further improving the efficiency of the CaL technology is how to prevent the gradual loss of capture capacity of limestone derived CaO as the number of carbonation/calcination cycles is increased. Natural dolomite (MgCa(CO3)2) has been proposed as an alternative sorbent precursor to limestone. Yet, carbonation of MgO is not thermodynamically favorable at CaL conditions, which may hinder the capture performance of dolomite. In the work described in this paper we carried out a thermogravimetric analysis on the multicyclic capture performance of natural dolomite under realistic regeneration conditions necessarily implying high calcination temperature, high CO2 concentration and fast transitions between the carbonation and calcination stages. Our study demonstrates that the sorbent derived from dolomite has a greater capture capacity as compared to limestone. SEM analysis shows that MgO grains in the decomposed dolomite are resistant to sintering under severe calcination conditions and segregate from CaO acting as a thermally stable support which mitigates the multicyclic loss of CaO conversion. Moreover, full decomposition of dolomite is achieved at significantly lower calcination temperatures as compared to limestone, which would help improving further the industrial competitiveness of the technology.Junta de Andalucía FQM-5735, TEP-7858, TEP-1900Ministerio de Economía y Competitividad FIS2011-25161, CTQ2011- 2762

The mOxy-CaL Process: Integration of Membrane Separation, Partial Oxy-combustion and Calcium Looping for CO2 Capture

CO2 capture and storage (CCS) is considered as a key strategy in the short to medium term to mitigate global warming. The Calcium-Looping process, based on the reversible carbonation/calcination of CaO particles, is a promising technology for post-combustion CO2 capture because of the low cost and non-toxicity of natural CaO precursors and the minor energy penalty on the power plant in comparison with amines capture based technologies (4-9 % compared to 8-12 %). Another interesting process to reduce CO2 emissions in power plants is oxy-combustion, which is based on replacing the air used for combustion by a highly concentrated (~95 % v/v) O2 stream. This work proposes a novel process (mOxy-CaL) for post-combustion CO2 capture based on the integration of membrane separation, partial oxy-combustion and the Calcium-Looping process. An oxygenenriched air stream, which is obtained from air separation by using highly permeable polymeric membranes, is used to carry out partial oxy-combustion. The flue gas exiting partial oxy-combustion shows a CO2 concentration of ~30 % v/v (higher than 15 % v/v typical in coal power plants). After that, the flue gas is passed to the CaL process where the CO2 reacts with CaO solids according to the carbonation reaction. Thermogravimetric analysis show that the multicycle CaO conversion is enhanced as the CO2 concentration in the flue gas stream is increased. Process simulations show that the mOxy-CaL process has a high CO2 capture efficiency (~95%) with lower energy consumption per kg of CO2 avoided than previously proposed post-combustion CO2 capture technologies. Moreover, the overall system size is significantly lower that state-of-the-art CaL systems, which allows for an important reduction in the capital cost of the technology

CO2 multicyclic capture of pretreated/doped CaO in the Ca-looping process. Theory and experiments

We study in this paper the conversion of CaO-based CO2 sorbents when subjected to repeated carbonation/calcination cycles with a focus on thermally pretreated/doped sorbents. Analytical equations are derived to describe the evolution of conversion with the cycle number from a unifying model based on the balance between surface area loss due to sintering in the loopingcalcination stage and surface area regeneration as a consequence of solid-state diffusion during the looping-carbonation stage. Multicyclic CaO conversion is governed by the evolution of surface area loss/regeneration that strongly depends on the initial state of the pore skeleton. In the case of thermally pretreated sorbents, the initial pore skeleton is highly sintered and regeneration is relevant whereas, for nonpretreated sorbents, the initial pore skeleton is soft and regeneration is negligible. Experimental results are obtained for sorbents subjected to a preheating controlled rate thermal analysis (CRTA) program. By applying this preheating program in a CO2 enriched atmosphere, CaO can be subjected to a rapid carbonation followed by a slow rate controlled decarbonation, which yields a highly sintered skeleton displaying a small conversion in the first cycle and self-reactivation in the next ones. Conversely, carbonation of the sorbent at a slow controlled rate enhances CO2 solid-state diffusion, which gives rise, after a quick decarbonation, to a highly porous skeleton. In this case, CaO conversion in the first cycle is very large but it decays abruptly in subsequent cycles. Data on CaO conversion retrieved from the literature and from further experimental measurements performed in our work are analyzed as influenced by a variety of experimental variables such as preheating temperature program, preheating exposition time, atmosphere composition, presence of additives, and carbonation/calcination conditions. Conversion data are well fitted by the proposed model equations, which are of help for a quantitative interpretation on the effect of experimental conditions on the multicyclic sorbent performance as a function of sintering/ regeneration parameters inferred from the fittings and allow foreseeing the critical conditions to promote reactivation. The peculiar behavior of some pretreated sorbents, showing a maximum of conversion at a small number of cycles, is explained in the light of the mode

Constant rate thermal analysis for thermal stability studies of polymers

This paper explores the relationship between the shapes of temperature-time curves obtained from experimental data recorded by means of constant rate thermal analysis (CRTA) and the kinetic model followed by the thermal degradation reaction. A detailed shape analysis of CRTA curves has been performed as a function of the most common kinetic models. The analysis has been validated with simulated data, and with experimental data recorded from the thermal degradation of polytetrafluoroethylene (PTFE), poly(1,4-butylene terephthalate) (PBT), polyethylene (PE) and poly(vinyl chloride) (PVC). The resulting temperature-time profiles indicate that the studied polymers decompose through phase boundary, random scission, diffusion and nucleation mechanisms respectively. The results here presented demonstrate that the strong dependence of the temperature-time profile on the reaction mechanism would allow the real kinetic model obeyed by a reaction to be discerned from a single CRTA curve.Junta de Andalucía TEP-03002Ministerio de Ciencia e Innovación MAT 2008-06619/MA

Enhancement of fast CO2Capture by a Nano-SiO2/CaO composite atCa-Looping conditions

In this paper we show the performance of a new CO2sorbentconsisting of a dry physical mixture of a Ca-based sorbent and a SiO2nanostructuredpowder. Thermo-gravimetric analysis (TGA) performed at conditions close to the Ca-looping process demonstrate that the rate of CO2capture by the mixture is enhancedduring the fast carbonation stage of practical interest in applications. Moreover, theresidual capture capacity of the mixture is increased. SEM/EDX, physisorption, andXRD analyses indicate that there is a relevant interaction between the nanostructuredSiO2skeleton and CaO at high temperatures, which serves to improve the efficiency ofthe transfer of CO2to small reactive pores as well as the stability of the sorbent porestructur

The Calcium-Looping (CaCO3/CaO) Process for Thermochemical Energy Storage in Concentrating Solar Power Plants

Articulo aceptado por la revista. * No publicado aún [28-06-2019]Energy storage based on thermochemical systems is gaining momentum as potential alternative to molten salts in Concentrating Solar Power (CSP) plants. This work is a detailed review about the promising integration of a CaCO3/CaO based system, the so-called Calcium-Looping (CaL) process, in CSP plants with tower technology. The CaL process relies on low cost, widely available and non-toxic natural materials (such as limestone or dolomite), which are necessary conditions for the commercial expansion of any energy storage technology at large scale. A comprehensive analysis of the advantages and challenges to be faced for the process to reach a commercial scale is carried out. The review includes a deep overview of reaction mechanisms and process integration schemes proposed in the recent literature. Enhancing the multicycle CaO conversion is a major challenge of the CaL process. Many lab-scale analyses carried out show that residual effective CaO conversion is highly dependent on the process conditions and CaO precursors used, reaching values as different as 0.07-0.82. The selection of the optimal operating conditions must be based on materials, process integration, technology and economics aspects. Global plant efficiencies over 45% (without considering solar-side losses) show the interest of the technology. Furthermore, the technological maturity and potential of the process is assessed. The direction towards which future works should be headed is discussed.Ministerio de Economia y Competitividad CTQ2014-52763-C2, CTQ2017- 83602-C2 (-1-R and -2-R)Unión Europea Horizon 2020 Grant agreement No 727348, project SOCRATCES

Role of precalcination and regeneration conditions on postcombustion CO2 capture in the Ca-looping technology

The Ca-looping (CaL) technology is already recognized as a potentially viable method to capture CO2 from postcombustion gas in coal fired power plants. In this process, CO2 is chemisorbed by CaO solid particles derived from precalcination of cheap and widely available natural limestone. The partially carbonated solids are regenerated by calcination under high CO2 concentration. Novel CaL concepts are proposed to further improve the efficiency of the technology such as the introduction of a recarbonation reactor in between the carbonation and calcination stages to mitigate the progressive deactivation of the regenerated CaO. Process simulations aimed at retrieving optimum design parameters and operating conditions to scale-up the technology yield results critically dependent on the multicyclic sorbent performance. Nevertheless, technical limitations usually preclude lab-scale tests from mimicking realistic CaL conditions necessarily involving high CO2 concentration for sorbent regeneration and quick transitions between carbonation and calcination. In this work, a lab-scale experimental analysis is reported on the CaO multicyclic conversion at CaL conditions closely resembling those to be expected in practice. The results presented evidence a relevant role of precalcination conditions. Precalcination in air leads to a strongly adverse effect on the activity of the sorbent regenerated under high CO2 concentration, which is further hindered if a recarbonation stage is introduced. On the other hand, sorbent deactivation is mitigated if precalcination is carried out at conditions similar to those used for sorbent regeneration. In this case, recarbonation helps lessening the loss of multicyclic conversion, which is further enhanced by the synergistic combination with heat pretreatment. Moreover, the present study shows that the kinetics of carbonation is strongly dependent on precalcination and regeneration conditions. The diffusion controlled carbonation phase and recarbonation are intensified if the sorbent is precalcined and regenerated under high CO2 concentration whereas the reaction controlled carbonation phase is notably hampered.Junta de Andalucía FQM-5735 TEP-7858España Mineco FIS2011-25161 CTQ2011-2762

Kissinger kinetic analysis of data obtained under different heating schedules

The dynamic heating rate method developed by TA Instruments ( Hi-Res ™ ) is a kind of sample controlled thermal analysis in which a linear relati onship between the logarith m of the heating rate and the rate of weight change is imposed. It is s hown in this paper that the reacted fraction at the maximum reaction rate strongly depends on the parameters selected for the Hi-Res heating algorithm, what invalidates the use of the Kissinger method for analysing Hi-Res data unless that the reaction fits a first order kinetic law. Only in this latter case, it has been demonstrated that it is not required that a constant value of the reacted fr action at the maximum reaction rate is fulfilled for determining the activation energy from the Kissi nger method. In such a case the Kissinger plot gives the real activation energy, independently of both the heating schedule used and the value of the reacted fraction, α m , at the maximum

Calcium-looping for post-combustion CO2 capture. On the adverse effect of sorbent regeneration under CO2

The multicyclic carbonation/calcination (c/c) of CaO solid particles at high temperature is at the basis of the recently emerged Calcium-looping (CaL) technology, which has been shown to be potentially suitable for achieving high and sustainable post-combustion CO2 capture efficiency. Despite the success of pilot plant projects at the MWth scale, a matter of concern for scaling-up the CaL technology to a commercial level (to the GWth scale) is that the CaO carbonation reactivity can be recovered only partially when the sorbent is regenerated by calcination at high temperatures (around 950 °C) as required by the CO2 high concentration in the calciner. In order to reactivate the sorbent, a novel CaL concept has been proposed wherein a recarbonator reactor operated at high temperature/high CO2 concentration leads to further carbonation of the solids before entering into the calciner for regeneration. Multicyclic thermogravimetric analysis (TGA) tests demonstrate the feasibility of recarbonation to reactivate the sorbent regenerated at high calcination temperatures yet at unrealistically low CO2 partial pressure mainly because of technical limitations concerning low heating/cooling rates. We report results from multicyclic c/c and carbonation/recarbonation/calcination (c/r/c) TGA tests at high heating/coling rates and in which the sorbent is regenerated in a dry atmosphere at high CO2 partial pressure. It is shown that at these conditions there is a drastic drop of CaO conversion to a very small residual value in just a few cycles. Moreover, the introduction of a recarbonation stage has actually an adverse effect. Arguably, CaCO3 decomposition in a CO2 rich atmosphere is ruled by CO2 dynamic adsorption/desorption in reactive CaO (1 1 1) surfaces as suggested by theoretical studies, which would preclude the growth of the regenerated CaO crystal structure along these reactive surfaces, and this effect would be intensified by recarbonation. Nevertheless, the presence of H2O in the calciner, which is also adsorbed/desorbed dynamically in CaO reactive planes, would shield CO2 adsorption/desorption thus mitigating the deeply detrimental effect of CO2 on the carbonation reactivity of the regenerated CaO structure. Oxy-combustion, which produces a significant amount of H2O, is currently used in pilot-scale plants to raise the temperature in the calciner. Auxiliary techniques are being explored to help heating the partially carbonated solids since oxyxombustion represents an important penalty to the CaL technology. Our study suggests that steam injection would be necessary in a dry calciner environment to avoid a sharp loss of CaO conversion if the sorbent is regenerated at high CO2 partial pressure.Junta de Andalucía FQM-5735 TEP-7858España Mineco Feder FIS2011-25161 CTQ2011-2762

Multicyclic conversion of limestone at Ca-looping conditions: The role of solid-sate diffusion controlled carbonation

Limestone derived CaO conversion when subjected to multiple carbonation/calcination cycles is a subject of interest currently fueled by several industrial applications of the so-called Ca-looping (CaL) technology. The multicyclic CaO conversion at Ca-looping conditions exhibits two main features as demonstrated by thermogravimetric analysis (TGA). On one hand, carbonation occurs by two well differentiated phases: a first kinetically-driven fast phase and a subsequent much slower solid-state diffusion controlled phase. On the other, carbonation in the fast phase usually shows a drastic decay with the cycle number along the first carbonation/calcination cycles. This trend can be reversed by means of heat pretreatment, which induces a marked loss of fast conversion in the first carbonation but enhances diffusion of CO2 in the solid. Upon decarbonation the regenerated CaO skeleton displays an increased conversion in the fast carbonation phase of the next cycle, a phenomenon which has been referred to as reactivation. Nonetheless, sorbent reactivation is hampered by looping carbonation/calcination conditions as those to be likely found in practice such as carbonation stages characterized by low CO2 concentrations and short duration and calcination stages at high temperatures in a CO2 enriched atmosphere, which causes a sintering and loss of activity of the regenerated CaO skeleton. We analyze in this work sorbent reactivation as affected by heat pretreatment and carbonation/calcination conditions. Aimed at shedding light on the role played by these conditions on reactivation we look separately at the multicyclic evolution of conversion in the kinetic and diffusive phases. Generally, the evolution of multicyclic conversion after the first cycle can be described by a balance between the surface area gain due to diffusive carbonation and the surface area loss as caused by sintering in the calcination stage. A significant gain of relative surface area after the first cycle, which is favored by harshening the heat pretreatment conditions, leads however to a marked decay of it during subsequent cycles, which precludes reactivation for an extended interval of cycles. On the other hand, sorbent grinding, if performed before heat pretreatment, leads to a less marked but more sustainable reactivation along the cycles. A novel observation reported in our work is that pretreatment of limestone in a CO 2 atmosphere leads upon a subsequent quick decarbonation to a CaO skeleton with extraordinarily enhanced reactivity in the kinetically-driven carbonation phase and with a high resistance to solid-state diffusion, which can be attributed to annealing of the crystal structure as reported by independent studies