Role of crystal structure on CO2 capture by limestone derived CaO subjected to carbonation/recarbonation/calcination cycles at Ca-looping conditions

[Display omitted] •CO2 capture of limestone subjected to carbonation/recarbonation/calcination cycles is affected by diffusion.•A reduction of crystallinity by ball milling favors diffusion and promotes recarbonation.•Thermal annealing enhances crystallinity and hinders recarbonation.•Milling promotes friability whereas annealing enhances the resistance of particles to fragmentation.•The solid crystal structure determines the efficiency of the novel Ca-looping concept. Large scale pilot plants are currently demonstrating the feasibility of the Calcium-looping (CaL) technology built on the multicyclic calcination/carbonation of natural limestone for post-combustion and pre-combustion CO2 capture. Yet, limestone derived CaO exhibits a drop of conversion when subjected to multiple carbonation/calcination cycles, which lessens the efficiency of the technology. In this paper we analyze a novel CaL concept recently proposed to mitigate this drawback based on the introduction of an intermediate stage wherein carbonation is intensified at high temperature and high CO2 partial pressure. It is shown that carbonation in this stage is mainly driven by solid-state diffusion, which is determined by the solid’s crystal structure. Accordingly, a reduction of crystallinity by ball milling, which favors diffusion, serves to promote recarbonation. Conversely, thermal annealing, which enhances crystallinity, hinders recarbonation. An initial fast phase has been identified in the recarbonation stage along which the rate of carbonation is also a function of the crystal structure indicating a relevant role of surface diffusion. This is consistent with a recently proposed mechanism for nucleation of CaCO3 on the CaO surface in islands with a critical size determined by surface diffusion. A further issue analyzed has been the effects of pretreatment and cycling on the mechanical strength of the material, whose fragility hampers the CaL process efficiency. Particle size distribution of samples dispersed in a liquid and subjected to high energy ultrasonic irradiation indicate that milling promotes friability whereas thermal annealing enhances the resistance of the particles to fragmentation even though pretreatment effects become blurred after cycling. Our study demonstrates that recarbonation conditions and crystal-structure controlled diffusion are important parameters to be considered in order to assess the efficiency of CO2 capture in the novel CaL concept.