Spray-Dried Sodium Zirconate: A Rapid Absorption Powder for CO₂ Capture with Enhanced Cyclic Stability

Improved powders for capturing CO₂ at high temperatures are required for H₂ production using sorption-enhanced steam reforming. Here, we examine the relationship between particle structure and carbonation rate for two types of Na₂ ZrO₃ powders. Hollow spray-dried microgranules with a wall thickness of 100-300 nm corresponding to the dimensions of the primary acetate-derived particles gave about 75 wt % theoretical CO₂ conversion after a process-relevant 5 min exposure to 15 vol % CO₂ . A conventional powder prepared by solid-state reaction carbonated more slowly, achieving only 50 % conversion owing to a greater proportion of the reaction requiring bulk diffusion through the densely agglomerated particles. The hollow granular structure of the spray-dried powder was retained postcarbonation but chemical segregation resulted in islands of an amorphous Na-rich phase (Na₂ CO₃ ) within a crystalline ZrO₂ particle matrix. Despite this phase separation, the reverse reaction to re-form Na₂ ZrO₃ could be achieved by heating each powder to 900 °C in N₂ (no dwell time). This resulted in a very stable multicycle performance in 40 cycle tests using thermogravimetric analysis for both powders. Kinetic analysis of thermogravimetric data showed the carbonation process fits an Avrami-Erofeyev 2 D nucleation and nuclei growth model, consistent with microstructural evidence of a surface-driven transformation. Thus, we demonstrate that spray drying is a viable processing route to enhance the carbon capture performance of Na₂ ZrO₃ powder.