Abstract: Calciumlooping method has been considered as one of the efficient options to capture CO₂ in the combustion flue gas. CaO-based sorbent is the basis for application of calcium looping and should be subjected to the severe calcination condition so as to obtain the concentrated CO₂ stream. In this research, CaO/CaZrO₃ sorbents were synthesized using the sol-gel combustion synthesis (SGCS) method with urea as fuel. The cyclic reaction performance of the synthesized sorbents was evaluated on a lab-scaled reactor system through calcination at 950℃ in a pure CO₂ atmosphere and carbonation at 650℃ in the 15% (by volume) CO₂. The mass ratio of CaO to CaZrO₃ as 8:2 (designated as Ca₈Zr₂) was screened as the best option among all the synthesized CaO sorbents for its high CO₂ capture capacity and carbonation conversion at the initial cycle. And then a gradual decay in the CO₂ capture capacity was observed at the following 10 successive cycles, but hereafter stabilized throughout the later cycles. Furthermore, structural evolution of the carbonated Ca₈Zr₂ over the looping cycles was investigated. With increasing looping cycles, the pore peak and mean grain size of the carbonated Ca₈Zr₂ sorbent shifted to the bigger direction but both the surface area (SA) ratio Φ and surface fractal dimension Ds decreased. Finally, morphological transformation of the carbonated Ca₈Zr₂ was observed. Agglomeration and edge rounding of the newly formed CaCO₃ grainswere found as aggravated at the cyclic carbonation stage. As a result, carbonation of Ca₈Zr₂ with CO₂was observed only confined to the external active CaO by the fast formation of the CaCO₃ shell outside, which occluded the further carbonation of the unreacted CaO inside. Therefore, enough attention should be paid to the carbonation stage and more effective activation measures should be explored to ensure the unreacted active CaO fully carbonated over the extended looping cycles.

Key words: CO₂ capture, Calcium looping cycles, CaO/CaO/CaZrO₃ sorbent, Sol-gel combustion synthesis method

摘要： Calciumlooping method has been considered as one of the efficient options to capture CO₂ in the combustion flue gas. CaO-based sorbent is the basis for application of calcium looping and should be subjected to the severe calcination condition so as to obtain the concentrated CO₂ stream. In this research, CaO/CaZrO₃ sorbents were synthesized using the sol-gel combustion synthesis (SGCS) method with urea as fuel. The cyclic reaction performance of the synthesized sorbents was evaluated on a lab-scaled reactor system through calcination at 950℃ in a pure CO₂ atmosphere and carbonation at 650℃ in the 15% (by volume) CO₂. The mass ratio of CaO to CaZrO₃ as 8:2 (designated as Ca₈Zr₂) was screened as the best option among all the synthesized CaO sorbents for its high CO₂ capture capacity and carbonation conversion at the initial cycle. And then a gradual decay in the CO₂ capture capacity was observed at the following 10 successive cycles, but hereafter stabilized throughout the later cycles. Furthermore, structural evolution of the carbonated Ca₈Zr₂ over the looping cycles was investigated. With increasing looping cycles, the pore peak and mean grain size of the carbonated Ca₈Zr₂ sorbent shifted to the bigger direction but both the surface area (SA) ratio Φ and surface fractal dimension Ds decreased. Finally, morphological transformation of the carbonated Ca₈Zr₂ was observed. Agglomeration and edge rounding of the newly formed CaCO₃ grainswere found as aggravated at the cyclic carbonation stage. As a result, carbonation of Ca₈Zr₂ with CO₂was observed only confined to the external active CaO by the fast formation of the CaCO₃ shell outside, which occluded the further carbonation of the unreacted CaO inside. Therefore, enough attention should be paid to the carbonation stage and more effective activation measures should be explored to ensure the unreacted active CaO fully carbonated over the extended looping cycles.

关键词: CO₂ capture, Calcium looping cycles, CaO/CaO/CaZrO₃ sorbent, Sol-gel combustion synthesis method