Ca-Rich Ca-Al-Oxide, High-Temperature-Stable Sorbents Prepared from Hydrotalcite Precursors: Synthesis, Characterization, and CO2 Capture Capacity

We present the design and synthesis of Ca-rich Ca-Al-O oxides, with Ca(2+)/Al(3+) ratios of 1:1, 3:1, 5:1, and 7:1, which were prepared by hydrothermal decomposition of coprecipitated hydrotalcite-like Ca-Al-CO(3) precursors, for high-temperature CO(2) adsorption at 500-700 degrees C. In situ X-ray diffraction measurements indicate that the coprecipitated, Ca-rich, hydrotalcite-like powders with Ca(2+)/Al(3+) ratios of 5:1 and 7:1 contained Ca(OH)(2) and layered double hydroxide (LDH) phases. Upon annealing, LDH was first destroyed at approximately 200 degrees C to form an amorphous matrix, and then at 450-550 degrees C, the Ca(OH)(2) phase was converted into a CaO matrix with incorporated Al(3+) to form a homogeneous solid solution without a disrupted lattice structure. CaO nanocrystals were grown by thermal treatment of the weakly crystalline Ca-Al-O oxide matrix. Thermogravimetric analysis indicates that a CO(2) adsorption capacity of approximately 51 wt.% can be obtained from Ca-rich Ca-Al-O oxides prepared by calcination of 7:1 Ca-Al-CO(3) LDH phases at 600-700 degrees C. Furthermore, a relatively high CO(2) capture capability can be achieved, even with gas flows containing very low CO(2) concentrations (CO(2)/N(2)=10%). Approximately 95.6% of the initial CO(2) adsorption capacity of the adsorbent is retained after 30 cycles of carbonationcalcination. TEM analysis indicates that carbonation-promoted CaCO(3) formation in the Ca-Al-O oxide matrix at 600 degrees C, but a subsequent desorption in N(2) at 700 degrees C, caused the formation CaO nanocrystals of approximately 10 nm. The CaO nanocrystals are widely distributed in the weakly crystalline Ca-Al-O oxide matrix and are present during the carbonationcalcination cycles. This demonstrates that Ca-Al-O sorbents that developed through the synthesis and calcination of Ca-rich Ca-Al LDH phases are suitable for long-term cyclic operation in severe temperature environments.